CN105358523A

CN105358523A - Polymerizable compound, polymerizable composition, and liquid crystal display element

Info

Publication number: CN105358523A
Application number: CN201480039005.3A
Authority: CN
Inventors: 小林雅秀; 后藤泰行; 小林孝弘
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2013-07-10
Filing date: 2014-03-13
Publication date: 2016-02-24
Anticipated expiration: 2034-03-13
Also published as: WO2015004947A1; TW201502249A; TWI648380B; JPWO2015004947A1; US10077401B2; TWI621696B; US20160152895A1; EP3020700A4; CN105358523B; KR20160030934A; EP3020700A1; JP6425041B2; EP3020700B1; TW201816091A

Abstract

Provided are: a polymerizable compound having a high polymerization reactivity, a high conversion rate and a high solubility in liquid crystal compositions; a polymerizable composition containing said compound; a liquid crystal composite prepared from said composition; and a liquid crystal display element having said composite. This polymerizable compound is configured in series form from three or four rings that are not fused together, and has three or more polymerizable groups, wherein at least one of said polymerizable groups is bonded to a ring that is not at either of the ends. This polymerizable composition contains the polymerizable compound and the liquid crystal composition. This liquid crystal composite is prepared from this polymerizable composition; a liquid crystal display element is also provided.

Description

Polymerizable compound, Polymerizable composition and liquid crystal display device

Technical field

The present invention relates to a kind of polymerizable compound, comprise liquid crystal complex body prepared by Polymerizable composition, the thus Polymerizable composition of this polymerizable compound and liquid-crystal composition, and liquid crystal display device.

Background technology

Optical anisotropy, dielectric anisotropy etc. that liquid crystal display device utilizes liquid crystal molecule in liquid-crystal composition to have.Phase transformation (phasechange is categorized as based on liquid crystal molecule pattern, PC) pattern, twisted nematic (twistednematic, TN) pattern, STN Super TN (supertwistednematic, STN) pattern, bistable state twisted nematic (bistabletwistednematic, BTN) pattern, electrically conerolled birefringence (electricallycontrolledbirefringence, ECB) pattern, optical compensation curved (opticallycompensatedbend, OCB) pattern, coplanar switching (in-planeswitching, IPS) pattern, fringing field switches (fringefieldswitching, FFS) pattern, vertical orientated (verticalalignment, VA) pattern etc.

Known in liquid-crystal composition combination have the liquid crystal display device of the pattern of polymkeric substance.It is such as polymer stabilizing orientation (polymersustainedalignment, PSA) or polymer stabilizing (polymerstabilized, PS) pattern.In the liquid crystal display device of described pattern, the liquid-crystal composition being added with polymerizable compound is injected display element.Between electrode, execute irradiation ultraviolet radiation under alive state and polymerizable compound is polymerized, making thus to generate polymkeric substance in liquid-crystal composition.Utilize this method can obtain time of response shortening, the improved liquid crystal display device of image retention of image.

Described method can be applicable to the liquid crystal display device of multiple operation mode, known PS-TN, PS-IPS, PS-FFS, PSA-VA, PSA-OCB isotype.The polymerizable compound used in the element of this kind of pattern is considered to make the ability of liquid crystal molecular orientation high, but the solubleness not very height in liquid-crystal composition.Though attempt so far improving the solubleness in liquid-crystal composition, if solubleness improves, then there is the tendency that polymerisation reactivity declines.Therefore, expect to develop the polymerizable compound having proper equilibrium between solubleness and polymerisation reactivity.

[prior art document]

[patent documentation]

Patent documentation 1: Japanese Patent Laid-Open 2012-18215 publication

Patent documentation 2: Japanese Patent Laid-Open 2013-14538 publication

Summary of the invention

[invention institute for solution problem]

Lesson One of the present invention is entitled as provides a kind of polymerizable compound, and it has high polymerisation reactivity, high conversion and the high-dissolvability in liquid-crystal composition.Second problem is for providing a kind of liquid crystal complex body, and it meets at least one of nematic high ceiling temperature, nematic low lower limit temperature, little viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant, the large physical property such as ratio resistance, suitable pre-dumping.Described problem provides a kind of liquid crystal complex body having proper equilibrium between at least two kinds of physical property.3rd problem is for providing a kind of liquid crystal display device, and it has the temperature range of broad used element, short response time, high voltage holding ratio, low threshold voltage, high-contrast and long lifetime.

[solving the means of problem]

The liquid crystal complex body that the present invention relates to a kind of polymerizable compound, comprise the Polymerizable composition of described polymerizable compound and liquid-crystal composition, prepared by described Polymerizable composition, and liquid crystal display device, this polymerizable compound comprises 3 or 4 rings mutually also not closing of series connection, and there is the polymerizability base of more than 3, wherein at least one polymerizability base and 3 or 4 rings is not that the ring key at two ends is tied.

[effect of invention]

The present invention first advantage is that polymerizable compound has high polymerisation reactivity, high conversion and the high-dissolvability in liquid-crystal composition.Second advantage is at least one that liquid crystal complex body meets nematic high ceiling temperature, nematic low lower limit temperature, little viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant, the large physical property such as ratio resistance, suitable pre-dumping.Described advantage is: liquid crystal complex body has suitable balance between at least two kinds of physical property.3rd advantage is: liquid crystal display device has the temperature range of broad used element, short response time, high voltage holding ratio, low threshold voltage, high-contrast and long lifetime.

Embodiment

In this specification sheets, the using method of term is as described below.Liquid crystal compounds is the general name of following non-polymerization compound, namely a non-polymerization compound of nematic phase, the equal mesomorphic phase of stratose is had, though and do not have a mesomorphic phase, in order to adjust the physical property of the liquid-crystal compositions such as ceiling temperature, lower limit temperature, viscosity, dielectric anisotropy and the non-polymerization compound be mixed into.Described compound has the six-ring such as Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, and its molecular structure is bar-shaped.Liquid-crystal composition is the mixture of liquid crystal compounds.Polymerizable compound is the compound inserting composition in order to generate polymkeric substance.Polymerizable composition is the composition comprising polymerizable compound, such as, be the mixture of polymerizable compound, liquid-crystal composition, additive etc.Liquid crystal complex body is the complex body generated by the polymerization of described Polymerizable composition.Liquid crystal display device is the general name of display panels and LCD MODULE.Nematic ceiling temperature is the transformation temperature of the nematic phase-isotropic phase of liquid-crystal composition, Polymerizable composition or liquid crystal complex body, is sometimes called for short ceiling temperature.Nematic lower limit temperature is called for short lower limit temperature sometimes.Difficulty when polymerisation reactivity refers to that reactant is polymerized.Transformation efficiency is the reactant that consumes because of the chemical reaction weight ratio relative to reactant.

Liquid-crystal composition is prepared by mixed solution crystalline compound.The ratio (content) of liquid crystal compounds is expressed as the weight percent (% by weight) of the weight based on liquid-crystal composition.Optionally add the additives such as optically active compound, antioxidant, UV light absorber, photostabilizer, thermo-stabilizer, defoamer, polymerization starter, polymerization retarder in the composition.The weight percent (% by weight) of the weight that the ratio (addition) of additive is same with the ratio of liquid crystal compounds to be expressed as based on liquid-crystal composition represents.Sometimes also operating weight PPM (ppm).The ratio of polymerization starter and polymerization retarder represents based on the weight of polymerizable compound exceptionally.

Sometimes by the compound represented by formula (1) referred to as compound (1).Described slightly note is also applicable to the represented compound such as formula (2).Compound (1) refers to a kind of compound represented by formula (1) or two or more compounds.In formula (1) ~ (8), by the A justified or sexangle surrounds ¹, B ¹, C ¹deng mark corresponding ring A respectively ¹, ring B ¹, ring C ¹deng.In formula (1), the oblique line of circle crosscut is referred to P ¹-S ¹base can select arbitrarily the binding site on ring.Described rule is also applicable to P ²-S ²base etc.Described rule is also applicable to the oblique line of the six-ring crosscut of formula (1-1) etc.The subscripts such as the middle a1 of formula (1) represent and ring A ¹etc. the quantity of the group of bond.When a1 is 2, ring A ¹on have two P ¹-S ¹base.Two P ¹-S ¹two groups of basis representation can identical or also can be different.Described rule be also applicable to when a1 is greater than 2 arbitrarily both.Described rule is also applicable to other groups.R ¹¹mark be used for formula (2), (3) etc. multimodal.Any two R in these compounds ¹¹two terminal group represented can identical or also can be different.In formula (8) during i=2, two mark D ¹exist in 1 formula.Two mark D in described compound ¹two rings represented can identical or also can be different.Described rule is also applicable to Z ¹⁷deng mark.

The statement of " at least one ' A ' can replace through ' B ' " refers to, when ' A ' quantity is 1, the position of ' A ' is that when ' A ' quantity is two or more, the position of these ' A ' also can unrestrictedly be selected arbitrarily.The statement of " at least one A can replace through B, C or D " comprises following situation: the situation that the situation that at least one A replaces through B, at least one A replace through C, and at least one A situation about replacing through D and then multiple A at least both situations about replacing in B, C, D.Such as, at least one-CH ₂-(or-CH ₂cH ₂-) alkyl that can replace through-O-(or-CH=CH-) comprises alkyl, thiazolinyl, alkoxyl group, alkoxyalkyl, alkoxyalkenyl, alkene oxygen base alkyl.In addition, continuous two-CH ₂-replace through-O-and form the ill-conditioned of-O-O-.In alkyl etc., methyl moiety (-CH ₂-H)-CH ₂-to replace and to become the situation of-O-H not good enough yet through-O-.

Fluoro-Isosorbide-5-Nitrae-the phenylene of 2-refers to following two kinds of divalent radicals.In chemical formula, fluorine can towards left (L), also can towards right (R).Described rule is also applicable to the divalent radical of the asymmetric ring as tetrahydropyrans-2,5-bis-base and so on.

The present invention comprises the content recorded in following project.

1. 1 kinds of polymerizable compounds, it comprise series connection not mutually and 3 or 4 rings closing, and have the polymerizability base of more than 3, wherein at least one polymerizability base and described 3 or 4 rings is not that the ring key at two ends is tied.

The polymerizable compound of item 2. according to item 1, it is represented by formula (1):

In formula (1),

P ¹, P ², P ³and P ⁴for polymerizability base;

S ¹, S ², S ³and S ⁴be independently the alkylidene group of singly-bound or carbon number 1 ~ 10, in described alkylidene group, at least one-CH ₂-can replace through-O-,-COO-,-OCO-or-OCOO-, at least one-CH ₂-CH ₂-can replace through-CH=CH-or-C ≡ C-, and at least one hydrogen can replace through fluorine or chlorine;

A1, a3 and a4 be independently 0,1,2,3 or 4, a2 be 1,2,3 or 4, and a1, a2, a3 and a4 and be 3 ~ 10;

Ring A ¹and ring A ⁴independent is phenyl, pyrimidyl, pyridyl, naphthyl, cyclohexyl, cyclohexenyl, THP trtrahydropyranyl or 1,3-alkyl dioxin, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen;

Ring A ²and ring A ³be independently 1, 4-phenylene, pyrimidine-2, 5-bis-base, pyridine-2, 5-bis-base, naphthalene-1, 2-bis-base, naphthalene-1, 3-bis-base, naphthalene-1, 4-bis-base, naphthalene-1, 5-bis-base, naphthalene-1, 6-bis-base, naphthalene-1, 7-bis-base, naphthalene-1, 8-bis-base, naphthalene-2, 3-bis-base, naphthalene-2, 6-bis-base, naphthalene-2, 7-bis-base, 1, 4-cyclohexylidene, 1, 4-phenylidene, tetrahydropyrans-2, 5-bis-base or 1, 3-diox-2, 5-bis-base, in these rings, at least one hydrogen can through halogen, the alkyl of carbon number 1 ~ 12, the alkoxyl group of carbon number 1 ~ 12, at least one hydrogen is through the alkyl of the carbon number 1 ~ 12 of halogen substiuted, or at least one hydrogen replaced through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted,

Z ¹, Z ²and Z ³be independently the alkylidene group of singly-bound or carbon number 1 ~ 10, in described alkylidene group, at least one-CH ₂-can replace through-O-,-CO-,-COO-or-OCO-, at least one-CH ₂-CH ₂-can through-CH=CH-,-C (CH ₃)=CH-,-CH=C (CH ₃)-or-C (CH ₃)=C (CH ₃)-replace, and at least one hydrogen can replace through fluorine or chlorine; And

B1 is 0 or 1.

The polymerizable compound of item 3. according to item 2, wherein in the formula (1) according to item 2,

P ¹, P ², P ²and P ⁴independent is acryloxy or methacryloxy;

S ¹, S ², S ³and S ⁴be independently the alkylidene group of singly-bound or carbon number 1 ~ 10, in described alkylidene group, 1-CH ₂-can replace through-O-,-COO-,-OCO-or-OCOO-, 1-CH ₂-CH ₂-can replace through-CH=CH-or-C ≡ C-, and at least one hydrogen can replace through fluorine or chlorine;

Ring A ¹and ring A ⁴independent is phenyl, pyrimidyl, pyridyl or naphthyl, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen;

Ring A ²and ring A ³independent is Isosorbide-5-Nitrae-phenylene, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,4-bis-base, naphthalene-1,5-bis-base, naphthalene-2,6-bis-base, 1,4-cyclohexylidene, tetrahydropyrans-2,5-bis-base or 1,3-diox-2,5-bis-base, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen;

Z ¹, Z ²and Z ³independent is singly-bound, the alkylidene group of carbon number 1 ~ 5 ,-CO-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-,-OCO-CH=CH-,-C (CH ₃)=CH-COO-,-OCO-CH=C (CH ₃)-,-CH=C (CH ₃)-COO-,-OCO-(CH ₃) C=CH-,-C (CH ₃)=C (CH ₃)-COO-,-OCO-C (CH ₃)=C (CH ₃)-,-CO-CH=CH-,-CH=CH-CO-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-,-OCH ₂-CH=CH-,-CH=CH-OCH ₂-or-CH ₂o-CH=CH-; And

B1 is 0 or 1.

The polymerizable compound of item 4. according to item 1 or 2, it is represented by formula (1-1):

In formula (1-1),

P ⁵, P ⁶, P ⁷and P ⁸independent is acryloxy or methacryloxy;

S ⁵, S ⁶, S ⁷and S ⁸be independently the alkylidene group of singly-bound or carbon number 1 ~ 5, in described alkylidene group, 1-CH ₂-can replace through-O-,-COO-or-OCO-, and 1-CH ₂-CH ₂-can replace through-CH=CH-;

C1, c3 and c4 be independently 0,1 or 2, c2 be 1 or 2, and c1, c2, c3 and c4 and be 3 ~ 6;

Ring A ⁵and ring A ⁸independent is phenyl, and wherein at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen;

Ring A ⁶and ring A ⁷be independently 1,4-phenylene, wherein at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen;

Z ⁴, Z ⁵and Z ⁶independent is singly-bound, the alkylidene group of carbon number 1 ~ 5 ,-CO-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-,-OCO-CH=CH-,-C (CH ₃)=CH-COO-,-OCO-CH=C (CH ₃)-,-CH=C (CH ₃)-COO-,-OCO-(CH ₃) C=CH-,-C (CH ₃)=C (CH ₃)-COO-,-OCO-C (CH ₃)=C (CH ₃)-,-CO-CH=CH-,-CH=CH-CO-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-,-OCH ₂-CH=CH-,-CH=CH-OCH ₂-or-CH ₂o-CH=CH-; And

D1 is 0 or 1.

5. polymerizable compounds according to item 1, its be by formula (1-1-1) or formula (1-1-2) any one represented by:

In formula (1-1-1) and formula (1-1-2),

P ⁹, P ¹⁰, P ¹¹, P ¹², P ¹³and P ¹⁴independent is acryloxy or methacryloxy;

S ¹¹, S ¹², S ¹³, S ¹⁴, S ¹⁵and S ¹⁶be independently the alkylidene group of singly-bound or carbon number 1 ~ 5, in described alkylidene group, 1-CH ₂-can replace through-O-,-COO-or-OCO-, and 1-CH ₂-CH ₂-can replace through-CH=CH-;

E1, e3 and e4 be independently 0,1 or 2, e2 be 1 or 2, and e1, e2, e3 and e4 and be 1 ~ 4;

Z ⁴, Z ⁵and Z ⁶independent is singly-bound, the alkylidene group of carbon number 1 ~ 5 ,-CO-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-,-OCO-CH=CH-,-C (CH ₃)=CH-COO-,-OCO-CH=C (CH ₃)-,-CH=C (CH ₃)-COO-,-OCO-(CH ₃) C=CH-,-C (CH ₃)=C (CH ₃)-COO-,-OCO-C (CH ₃)=C (CH ₃)-,-CO-CH=CH-,-CH=CH-CO-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-,-OCH ₂-CH=CH-,-CH=CH-OCH ₂-or-CH ₂o-CH=CH-;

G1 is 0,1 or 2; And

Y ¹for the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 5, carbon number 1 ~ 5, at least one hydrogen are through the alkyl of the carbon number 1 ~ 5 of halogen substiuted or at least one the hydrogen alkoxyl group through the carbon number 1 ~ 5 of halogen substiuted.

The polymerizable compound of item 6. according to item 1 or 2, it is represented by formula (1-2) or (1-3):

In formula (1-2) and formula (1-3),

S ⁹, S ¹⁰, S ¹¹, S ¹², S ¹³and S ¹⁴be independently the alkylidene group of singly-bound or carbon number 1 ~ 5, in described alkylidene group, 1-CH ₂-can replace through-O-,-COO-or-OCO-, and 1-CH ₂-CH ₂-can replace through-CH=CH-;

Z ⁷, Z ⁸and Z ⁹independent is singly-bound, the alkylidene group of carbon number 1 ~ 5 ,-CO-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-,-OCO-CH=CH-,-C (CH ₃)=CH-COO-,-OCO-CH=C (CH ₃)-,-CH=C (CH ₃)-COO-,-OCO-(CH ₃) C=CH-,-C (CH ₃)=C (CH ₃)-COO-,-OCO-C (CH ₃)=C (CH ₃)-,-CO-CH=CH-,-CH=CH-CO-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-,-OCH ₂-CH=CH-,-CH=CH-OCH ₂-or-CH ₂o-CH=CH-.

The polymerizable compound of item 7. according to item 1 or 2, it is represented by formula (1-4) or (1-5):

In formula (1-4) and formula (1-5),

P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy;

Y ¹for the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 5, carbon number 1 ~ 5, at least one hydrogen are through the alkyl of the carbon number 1 ~ 5 of halogen substiuted or at least one the hydrogen alkoxyl group through the carbon number 1 ~ 5 of halogen substiuted;

S ⁹, S ¹¹and S ¹⁴independent is singly-bound ,-CH ₂-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CH=CH-,-C ≡ C-,-CH ₂cH ₂o-,-OCH ₂cH ₂-,-CH=CH-O-or-O-CH=CH-;

E1 is 1 or 2, and e2 is 0,1 or 2;

Z ⁷, Z ⁸and Z ⁹independent is singly-bound ,-CO-,-COO-,-CH=CH-,-CH=CH-COO-,-C (CH ₃)=CH-COO-,-CH=C (CH ₃)-COO-,-C (CH ₃)=C (CH ₃)-COO-,-COCH=CH-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-or-CH=CH-OCH ₂-.

The polymerizable compound of item 8. according to item 7, wherein in formula (1-4) or (1-5), P ⁹, an e1 P ¹¹and P ¹⁴in at least one is acryloxy, and at least one is methacryloxy.

The polymerizable compound of item 9. according to item 1 or 2, it is represented by formula (1-6) or (1-7):

In formula (1-6) and formula (1-7), P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy;

Y ²for the alkyl of halogen, carbon number 1 ~ 5, the alkoxyl group of carbon number 1 ~ 5; And f1 be 1 or 2, f2 be 0,1 or 2.

The polymerizable compound of item 10. according to item 9, wherein in formula (1-6) or (1-7), P ⁹, a f1 P ¹¹and P ¹⁴in at least one is acryloxy, and at least one is methacryloxy.

The polymerizable compound of item 11. according to item 1 or 2, it is represented by formula (1-8) or (1-9):

In formula (1-8) or formula (1-9), P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy, and g1 is 1 or 2.

Item 12. 1 kinds of Polymerizable compositions, it contains the compound of at least one according to any one of item 1 ~ 11.

13. Polymerizable compositions according to item 12, at least one compound in its cohort also containing the compound be selected from represented by formula (2) ~ (4):

In formula (2) ~ (4),

R ¹¹and R ¹²independent is the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in described alkyl or thiazolinyl, and at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

Ring B ¹, ring B ², ring B ³and ring B ⁴independent is Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene, the fluoro-Isosorbide-5-Nitrae-phenylene of 2-, 2,5-bis-fluoro-Isosorbide-5-Nitrae-phenylenes or pyrimidine-2,5-bis-base;

Z ¹¹, Z ¹²and Z ¹³independent is singly-bound ,-CH ₂cH ₂-,-CH=CH-,-C ≡ C-or-COO-.

14. Polymerizable compositions according to item 12 or 13, at least one compound in its cohort also containing the compound be selected from represented by formula (5) ~ (7):

In formula (5) ~ (7),

R ¹³for the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in described alkyl or thiazolinyl, at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

X ¹¹for fluorine, chlorine ,-OCF ₃,-OCHF ₂,-CF ₃,-CHF ₂,-CH ₂f ,-OCF ₂cHF ₂or-OCF ₂cHFCF ₃;

Ring C ¹, ring C ²and ring C ³independent is Isosorbide-5-Nitrae-cyclohexylidene, at least one hydrogen can through the Isosorbide-5-Nitrae-phenylene of fluorine replacement, tetrahydropyrans-2,5-bis-base, 1,3-diox-2,5-bis-base or pyrimidine-2,5-bis-base;

Z ¹⁴, Z ¹⁵and Z ¹⁶independent is singly-bound ,-CH ₂cH ₂-,-CH=CH-,-C ≡ C-,-COO-,-CF ₂o-,-OCF ₂-,-CH ₂o-or-(CH ₂) ₄-; And

L ¹¹and L ¹²independent is hydrogen or fluorine.

15. Polymerizable compositions according to any one of item 12 ~ 14, at least one compound in its cohort also containing the compound be selected from represented by formula (8):

In formula (8), R ¹⁴for the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in alkyl or alkenyl, at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

X ¹²for-C ≡ N or-C ≡ C-C ≡ N;

Ring D ¹for Isosorbide-5-Nitrae-phenylene, tetrahydropyrans-2,5-bis-base, 1,3-diox-2,5-bis-base or pyrimidine-2,5-bis-base that Isosorbide-5-Nitrae-cyclohexylidene, at least one hydrogen can replace through fluorine;

Z ¹⁷for singly-bound ,-CH ₂cH ₂-,-C ≡ C-,-COO-,-CF ₂o-,-OCF ₂-or-CH ₂o-;

L ¹³and L ¹⁴independent is hydrogen or fluorine; And

I is 1,2,3 or 4.

Item 16. 1 kinds of liquid crystal complex bodys, it is generated by the polymerization of the Polymerizable composition according to any one of item 12 ~ 15.

Item 17. 1 kinds of optically anisotropic bodies, it is generated by the polymerization of the Polymerizable composition according to any one of item 12 ~ 15.

Item 18. 1 kinds of liquid crystal display device, it is containing the Polymerizable composition according to any one of with good grounds item 12 ~ 15 or the liquid crystal complex body according to item 15.

Item 19. 1 kinds is selected from the purposes of at least one in the cohort of compound, the Polymerizable composition according to any one of item 12 ~ 15 and the liquid crystal complex body according to item 16 according to any one of item 1 ~ 11, and it is for liquid crystal display device.

The present invention also comprises the following.A () described Polymerizable composition, it also contains at least one of the additives such as optically active compound, antioxidant, UV light absorber, photostabilizer, thermo-stabilizer, defoamer, polymerization starter, polymerization retarder.(b) described Polymerizable composition, its polymerizable compound also containing the compound differed from represented by formula (1).C () a kind of active matrix (activematrix, AM) element, it contains described Polymerizable composition.D () a kind of element, it contains described Polymerizable composition, and has PS-TN, PS-IPS, PS-FFS, PSA-VA or PSA-OCB pattern.E () a kind of infiltration type element, it contains described Polymerizable composition.(f) using described Polymerizable composition as the purposes with nematic composition.(g) by adding optically active compound in the composition as the purposes of optical activity composition.

The present invention also comprises the following.(h) a kind of Polymerizable composition, at least one compound in the cohort containing the compound be selected from represented by formula (1), and there is positive dielectric anisotropy.(i) a kind of Polymerizable composition, at least one compound in cohort containing the compound be selected from represented by formula (1), at least one compound be selected from the cohort of the compound represented by formula (2) ~ (4), and be selected from least one compound in the cohort of the compound represented by formula (5) ~ (7).(j) a kind of Polymerizable composition, at least one compound in cohort containing the compound be selected from represented by formula (1), at least one compound be selected from the cohort of the compound represented by formula (2) ~ (4), and be selected from least one compound in the cohort of the compound represented by formula (8).(k) a kind of Polymerizable composition, at least one compound in cohort containing the compound be selected from represented by formula (1), at least one compound be selected from the cohort of the compound represented by formula (2) ~ (4), at least one compound be selected from the cohort of the compound represented by formula (5) ~ (7), and be selected from least one compound in the cohort of the compound represented by formula (8).L () described Polymerizable composition, also contains tool 2,3-difluoro phenylene and dielectric anisotropy is negative liquid crystal compounds.M () a kind of liquid crystal complex body, is generated by the polymerization of described Polymerizable composition.N the purposes of () described Polymerizable composition or described liquid crystal complex body, it is for having the liquid crystal display device of PSA pattern.

1. polymerizable compound

First polymerizable compound of the present invention is described, then illustrates with the order of synthesis method, Polymerizable composition, liquid crystal complex body, liquid crystal display device.Described polymerizable compound comprise series connection not mutually and 3 or 4 rings closed, and having the polymerizability base of more than 3, is not wherein that the ring key at two ends is tied at least one polymerizability base and 3 or 4 rings.Herein, ring can be and cyclization, and by described and cyclization in-vivo counting is 1 ring when cyclization.

The typical case of described polymerizable compound is the following compound that formula (1) represents.The first, compound (1) has the feature with rodlike molecule structure.The liquid-crystal composition that commercially available liquid crystal display device uses is the mixture of the liquid crystal compounds of tool rodlike molecule structure.The molecular structure of compound (1) and the molecular structure of liquid crystal compounds similar.Therefore compound (1) has the high-dissolvability in liquid-crystal composition.The second, compound (1) has the feature of the group comprising tool height polymerizability.The example of this kind of polymerizability base is acryloxy or methacryloxy.Compound (1) has at least three polymerizability bases.Therefore, the symmetry of molecule declines, and therefore expects that the solubleness in liquid-crystal composition improves.

In formula (1), P ¹, P ², P ³and P ⁴for polymerizability base.The preference of polymerizability base is acryloxy, methacryloxy, acrylamide, Methacrylamide, vinyloxy group, vinyl carbonyl, oxirane base, oxetanyl, 3,4-epoxycyclohexyls or maleimide.In these groups, at least one hydrogen can replace through fluorine.More preferably example is-OCO-(M ¹) C=CH (M ²), herein, M ¹and M ²independent is hydrogen, fluorine ,-CH ₃or-CF ₃.Preferred M ¹or M ²for hydrogen or-CH ₃.Particularly preferred example is acryloxy (-OCO-HC=CH ₂) or methacryloxy (-OCO-(CH ₃) C=CH ₂).

In formula (1), S ¹, S ², S ³and S ⁴be independently the alkylidene group of singly-bound or carbon number 1 ~ 10, in described alkylidene group, at least one-CH ₂-can replace through-O-,-COO-,-OCO-or-OCOO-, at least one-CH ₂-CH ₂-can replace through-CH=CH-or-C ≡ C-, and at least one hydrogen can replace through fluorine or chlorine.

S ¹, S ², S ³or S ⁴preference be: singly-bound ,-CH ₂-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CH ₂cH ₂-,-CH=CH-,-C ≡ C-,-(CH ₂) ₃-,-CH ₂cH ₂o-,-OCH ₂cH ₂-,-CH=CH-O-,-O-CH=CH-,-C ≡ C-O-,-O-C ≡ C-,-(CH ₂) ₄-,-(CH ₂) ₃-O-,-O-(CH ₂) ₃-,-(CH ₂) ₄o-or-O (CH ₂) ₄-.More preferably example is: singly-bound ,-CH ₂-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CH=CH-,-C ≡ C-,-CH ₂cH ₂o-,-OCH ₂cH ₂-,-CH=CH-O-or-O-CH=CH-.Particularly preferred example is: singly-bound ,-CH ₂-,-CH=CH-,-CH=CH-O-,-O-CH=CH-,-CH ₂cH ₂o-or-OCH ₂cH ₂-.Most preferably example is singly-bound.The steric configuration of the double bond of-CH=CH-can be cis, also can be trans.Transly be better than cis.

In formula (1), a1, a3 and a4 be independently 0,1,2,3 or 4, a2 be 1,2,3 or 4, a1, a2, a3 and a4 and be 3 ~ 10.Because a2 is more than 1, so be not the ring A at two ends ²there is at least one polymerizability base.The preference of a1, a3 or a4 is 1 or 2.The preference of a2 is 1 or 2.

In formula (1), ring A ¹and ring A ⁴independent is phenyl, pyrimidyl, pyridyl, naphthyl, cyclohexyl, cyclohexenyl, THP trtrahydropyranyl or 1,3-alkyl dioxin, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted through the alkyl of the carbon number 1 ~ 12 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 12, carbon number 1 ~ 12, at least one hydrogen.

Ring A ¹or ring A ⁴preference be phenyl, naphthyl or cyclohexyl, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 3 of halogen substiuted through the alkyl of the carbon number 1 ~ 3 of halogen substiuted or at least one hydrogen through fluorine, chlorine, at least one hydrogen.More preferably example is phenyl or naphthyl, in these rings, at least one hydrogen can replace through the alkoxyl group of the carbon number 1 ~ 5 of halogen substiuted through the alkyl of the carbon number 1 ~ 5 of halogen substiuted or at least one hydrogen through the alkoxyl group of the alkyl of fluorine, chlorine, carbon number 1 ~ 5, carbon number 1 ~ 5, at least one hydrogen.At least one hydrogen described is-CH through the preference of the alkyl of halogen substiuted ₂f ,-CHF ₂,-CF ₃,-CClF ₂,-CH ₂cF ₃,-CF ₂cF ₃or-CH ₂h ₂cF ₃.Particularly preferred example is phenyl.

Ring A ²and ring A ³be independently 1, 4-phenylene, pyrimidine-2, 5-bis-base, pyridine-2, 5-bis-base, naphthalene-1, 2-bis-base, naphthalene-1, 3-bis-base, naphthalene-1, 4-bis-base, naphthalene-1, 5-bis-base, naphthalene-1, 6-bis-base, naphthalene-1, 7-bis-base, naphthalene-1, 8-bis-base, naphthalene-2, 3-bis-base, naphthalene-2, 6-bis-base, naphthalene-2, 7-bis-base, 1, 4-cyclohexylidene, 1, 4-phenylidene, tetrahydropyrans-2, 5-bis-base or 1, 3-diox-2, 5-bis-base, in these rings, at least one hydrogen can through halogen, the alkyl of carbon number 1 ~ 12, the alkoxyl group of carbon number 1 ~ 12, at least one hydrogen is through the alkyl of the carbon number 1 ~ 12 of halogen substiuted, or at least one hydrogen replaced through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted.

Ring A ²or ring A ³preference be Isosorbide-5-Nitrae-phenylene, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-Isosorbide-5-Nitrae-two base, naphthalene-1,5-bis-base, naphthalene-1,6-bis-base, naphthalene-2,6-bis-base, Isosorbide-5-Nitrae-cyclohexylidene, tetrahydropyrans-2,5-bis-base or 1,3-diox-2,5-bis-base, in these rings, at least one or two hydrogen can replace through the alkyl of the carbon number 1 ~ 3 of halogen substiuted through the alkyl of fluorine, chlorine, carbon number 1 ~ 3 or at least one hydrogen.

Ring A ²or ring A ³more preferably example be: 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-bis-fluoro-1, 4-phenylene, 2, 5-bis-fluoro-1, 4-phenylene, 2, 6-bis-fluoro-1, 4-phenylene, 2-chloro-1, 4-phenylene, the chloro-3-of 2-fluoro-1, 4-phenylene, 2-methyl isophthalic acid, 4-phenylene, 2-ethyl-1, 4-phenylene, 2-sec.-propyl-1, 4-phenylene, the 2-tertiary butyl-1, 4-phenylene, 2-methoxyl group-1, 4-phenylene, 2-oxyethyl group-1, 4-phenylene, 2-propoxy--1, 4-phenylene, 2-butoxy-1, 4-phenylene, 2-difluoromethyl-1, 4-phenylene, 2-Trifluoromethyl-1, 4-phenylene, pyrimidine-2, 5-bis-base or pyridine-2, 5-bis-base.And then more preferably example is: naphthalene-Isosorbide-5-Nitrae-two base, naphthalene-1,5-bis-base, naphthalene-1,6-bis-base or naphthalene-2,6-bis-base.Particularly preferred example is: Isosorbide-5-Nitrae-phenylene, naphthalene-Isosorbide-5-Nitrae-two base, naphthalene-1,5-bis-base or naphthalene-2,6-bis-base.Most preferably example is Isosorbide-5-Nitrae-phenylene.

In formula (1), Z ¹, Z ²and Z ³be independently the alkylidene group of singly-bound or carbon number 1 ~ 10, in described alkylidene group, at least one-CH ₂-can replace through-O-,-CO-,-COO-or-OCO-, at least one-CH ₂-CH ₂-can through-CH=CH-,-C (CH ₃)=CH-,-CH=C (CH ₃)-or-C (CH ₃)=C (CH ₃)-replace, and at least one hydrogen can replace through fluorine or chlorine.

Z ¹, Z ²or Z ³preference be: the alkylidene group of singly-bound, carbon number 1 ~ 5 ,-CO-,-COO-,-OCO-,-CH=CH-,-CH=CH-COO-,-OCO-CH=CH-,-C (CH ₃)=CH-COO-,-OCO-CH=C (CH ₃)-,-CH=C (CH ₃)-COO-,-OCO-(CH ₃) C=CH-,-C (CH ₃)=C (CH ₃)-COO-,-OCO-C (CH ₃)=C (CH ₃)-,-CO-CH=CH-,-CH=CH-CO-,-C (CH ₃)=C (CH ₃)-,-CH=CH-CH ₂o-,-OCH ₂-CH=CH-,-CH=CH-OCH ₂-or-CH ₂o-CH=CH-.More preferably example is singly-bound ,-COO-,-OCO-or-CH=CH-.Most preferably example is singly-bound.When these have-CH=CH-in conjunction with base, steric configuration can be cis, or also can be trans.Preferred steric configuration is trans.

In formula (1), b1 is 0 or 1.The preference of b1 is 0.

Polymerizability base P, concatenating group S in compound (1), ring A and in conjunction with base Z preference as above.Described example is also applicable to the next chemical formula of compound (1).Suitable selective polymerization base (P is carried out with reference to described preference ¹~ P ⁴), concatenating group (S ¹~ S ⁴), ring (A ¹~ A ⁴) and in conjunction with base (Z ¹~ Z ³) combination, the polymerizable compound with target properties can be obtained.In addition, with P ¹the S of bond ¹element be the ill-conditioned of oxygen.Its reason is to generate the divalent radical as-COO-O-,-O-O-and so on.Described rule is also applicable to P ²with S ²bond etc.Physical property due to compound there is no large difference, so compound (1) can comprise more compared with the amount of natural abundance ²h (deuterium), ¹³the isotropic substances such as C.

The preference of compound (1) is compound (1-1).More preferably example is compound (1-2) or (1-3).And then more preferably example is compound (1-4) or (1-5).Particularly preferred example can lift compound (1-2-a) ~ (1-2-i), compound (1-3-a) ~ (1-3-g), (1-4-a) ~ (1-4-f) and (1-5-a) ~ (1-5-g).

In compound (1-2-a) ~ (1-2-i), compound (1-3-a) ~ (1-3-g), compound (1-4-a) ~ (1-4-f) and compound (1-5-a) ~ (1-5-g), P ⁹, P ¹⁰, P ¹¹, P ¹², P ¹³and P ¹⁴independent is acryloxy or methacryloxy; S ⁹, S ¹⁰, S ¹¹, S ¹², S ¹³and S ¹⁴independent is singly-bound ,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-CH=CH-,-C ≡ C-,-CH ₂cH ₂o-,-OCH ₂cH ₂-,-CH=CH-O-or-O-CH=CH-; Y ¹for the alkoxyl group of the alkyl of halogen, carbon number 1 ~ 5, carbon number 1 ~ 5, at least one hydrogen are through the alkyl of the carbon number 1 ~ 5 of halogen substiuted or at least one the hydrogen alkoxyl group through the carbon number 1 ~ 5 of halogen substiuted; And

The P of compound (1-2-a) ~ (1-2-i), compound (1-3-a) ~ (1-3-g), compound (1-4-a) ~ (1-4-f) and compound (1-5-a) ~ (1-5-g) ⁹, P ¹⁰, P ¹¹, P ¹², P ¹³and P ¹⁴independent is acryloxy or methacryloxy; S ⁹, S ¹⁰, S ¹¹, S ¹², S ¹³and S ¹⁴for singly-bound; Z ⁷, Z ⁸and Z ⁹for during singly-bound most preferably.In these compounds, preference is: compound (1-2-a), compound (1-2-b), compound (1-2-c), compound (1-2-d), compound (1-3-a), compound (1-3-b), compound (1-3-d), compound (1-3-e), compound (1-3-g), compound (1-4-a), compound (1-4-b), compound (1-5-a) or compound (1-5-b).More preferably example is compound (1-3-a), compound (1-3-b) or compound (1-5-a).

In addition, in compound (1-4-a), (1-4-b), (1-5-a) and (1-5-b), Y is worked as ¹for halogen, P ⁹, 1 or 2 P ¹¹and P ¹⁴in at least one is acryloxy, and when at least one is methacryloxy, the solubleness in liquid-crystal composition caused by the symmetry of molecule declines improves also to be expected, so preferably.

2. synthesis method

The synthesis method of compound (1) is described.Compound (1) is by synthesizing appropriately combined for the method for Synthetic Organic Chemistry.Target terminal group is imported in initial substance, ring and be recorded in Hou Ben-Huai Er (Houben-Wyle in conjunction with the method for base, " organic chemistry procedures (MethodenderOrganischeChemie) ", George Di Mu press (Georg-ThiemeVerlag), Stuttgart (Stuttgart)), " organic synthesis " (OrganicSyntheses, John Wei Li father and son publishing company (JohnWily & Sons, Inc.)), " organic reaction " (OrganicReactions, John Wei Li father and son publishing company), " comprehensive organic synthesis " (ComprehensiveOrganicSynthesis, Pei Geman publishing company (PergamonPress)), in the books such as new experimental chemistry lecture (ball is apt to).

2-1. is in conjunction with the generation of base Z

Generate in compound (1) in conjunction with base Z ¹~ Z ³the example of method as shown in following flow process.In described flow process, MSG ¹(or MSG ²) for having any monovalent organic radical of at least one ring.Multiple MSG ¹(or MSG ²) represented by any monovalent organic radical can identical or also can be different.Compound (1A) ~ (1I) is equivalent to compound (1).There is shown in the generation of ester the synthesis method of the compound of-COO-.The compound with-OCO-also can utilize described synthesis method to synthesize.Asymmetrical also identical in conjunction with base for other.

(1) generation of singly-bound

In carbonate aqueous solution, under the existence of the catalyzer of tetrakis triphenylphosphine palladium and so on, aryl boric acid (21) is made to carry out reacting and synthetic compound (1A) with the compound (22) synthesized with all perception methods.Described compound (1A) is also by making the compound (23) synthesized with all perception methods react with n-Butyl Lithium, then react with zinc chloride, under the existence of the catalyzer of two (triphenylphosphine) palladium of dichloro and so on, make compound (22) carry out reacting synthesizing.

(2) generation of-COO-

Compound (23) and n-Butyl Lithium are reacted, then with carbon dioxide reaction and obtain carboxylic acid (24).1,3-dicyclohexylcarbodiimide (1,3-dicyclohexylcarbodiimide, and N DCC), N-dimethyl-4-aminopyridine (N, N-dimethyl-4-aminopyridine, DMAP) existence under, make compound (24) and the phenol (25) synthesized with all perception methods carry out dehydrating condensation and synthetic compound (1B).

(3)-CF ₂the generation of O-

Compound (26) is obtained with the vulcanizing agent process compound (1B) of lawesson reagent (Lawesson'sreagent) and so on.With hydrogen fluoride pyridine complex compound and N-bromo-succinimide (NBS), compound (26) is fluoridized and synthetic compound (1C).Can refer to " Chemistry Letters (Chem.Lett.) " the 827th phase in 1992 of the people such as the black star of M. (M.Kuroboshi).Also with (diethylamino) sulfur trifluoride ((diethylamino) sulfurtrifluoride, DAST) compound (26) fluoridized and carry out synthetic compound (1C).Can refer to the phase " organic chemistry periodical (JournalofOrganicChemistry, J.Org.Chem.) " nineteen ninety the 55th the 768th page of the people such as W.H. class Neil (W.H.Bunnelle).Also Pierre can be utilized. the method that " the international English edition (AngewandteChemieInternationalEditioninEnglish, Angew.Chem.Int.Ed.) of applied chemistry " of Leo Kirch (Peer.Kirsch) etc. was recorded in phase calendar year 2001 the 40th the 1480th page is described in conjunction with base to generate.

(4) generation of-CH=CH-

After n-Butyl Lithium process compound (22), obtain aldehyde (28) with formamide such as DMFs (DMF).With the alkali of tertiary butyl alcohol potassium and so on, the phosphonium salt synthesized with all perception methods (27) processed and produce phosphorus ylide (phosphorusylide), described phosphorus ylide and aldehyde (28) being reacted and carrys out synthetic compound (1D).Cis body can be generated according to reaction conditions, therefore can optionally utilize known method, cis body isomery is turned to trans body.

(5)-CH ₂the generation of O-

With reductive agents such as sodium borohydrides, compound (28) reduction is obtained compound (29).With Hydrogen bromide etc., described compound (29) carried out halogenation and obtain compound (31).Under salt of wormwood etc. exists, compound (31) and compound (30) are reacted and synthetic compound (1E).

(6) generation of-CH=CH-COO-

Make the alkali such as sodium hydride act on diethylphosphonoacetic acid ethyl ester to prepare phosphorus ylide, make described phosphorus ylide and aldehyde (32) carry out reacting and obtaining ester (33).Under the existence of the alkali such as sodium hydroxide, ester (33) is hydrolyzed and obtains carboxylic acid (34).Make described compound and compound (25) carry out dehydrating condensation and carry out synthetic compound (1F).

(7)-C (CH ₃the generation of)=CH-COO-

Make the alkali such as sodium hydride act on diethylphosphonoacetic acid ethyl ester to prepare phosphorus ylide, make described phosphorus ylide and methyl ketone (35) carry out reacting and obtaining ester (36).Then under the existence of the alkali such as sodium hydroxide, ester (36) be hydrolyzed and obtain carboxylic acid (37), then by carrying out synthetic compound (1G) with the dehydrating condensation of compound (25).

(8)-CH=C (CH ₃) generation of-COO-

At N, N-dicyclohexylmethylamine (Cy ₂under the existence of the catalyzer of alkali and two (three-tertiary butyl phosphine) palladium and so on NMe) and so on, make the compound (38) synthesized with all perception methods carry out reaction with the compound (39) synthesized with all perception methods and carry out synthetic compound (1H).

(9)-C (CH ₃)=C (CH ₃) generation of-COO-

Compound (40) is obtained by making compound (25) and pyruvic acid dehydrating condensation.Under zinc and titanium tetrachloride exist, compound (40) and compound (35) are reacted, and synthetic compound (1I).

The generation of 2-2. concatenating group S

Polymerizability base is-OCO-(M ¹) C=CH (M ²) compound in, be described with item (1) ~ (5) method of formation to concatenating group S.With item (6), the compound that polymerizability base is the vinyloxy group (P-2) be substituted or the allyloxy (P-3) be substituted is described.

(1) singly-bound

Generate the example of the method for the compound (1) that concatenating group S is singly-bound as shown in following flow process.In described flow process, MSG ¹for having any monovalent organic radical of at least one ring.Compound (1J) ~ (1M) is equivalent to compound (1).

At M ¹and M ²be not all-CF ₃situation, M ¹for fluorine and M ²be not-CF ₃situation or M ¹for-CF ₃and M ²when not being fluorine, commercially available have the carboxylic acid (41) shown in above flow process.Under the existence of DCC and DMAP, make described carboxylic acid (41) and compound (30) carry out dehydrating condensation carry out synthetic compound (1J).

At M ¹and M ²be-CF ₃when, under the existence of DCC and DMAP, make carboxylic acid (42) and compound (30) carry out dehydrating condensation and obtain compound (43).Under the existence of cupric iodide catalyst, make compound (43) and 2,2-bis-fluoro-2-(fluorosulfonyl) methyl acetates carry out reaction and carry out synthetic compound (1K).

At M ¹for fluorine and M ²for-CF ₃when, under DCC and DMAP exists, make carboxylic acid (44) and compound (30) dehydrating condensation and obtain compound (45).With fluorizating agents such as DST, compound (45) is fluoridized and obtained compound (46).Compound (46) and 2,2-bis-fluoro-2-(fluorosulfonyl) methyl acetates Reactive Synthesis compound (1L) are made under the existence of cupric iodide catalyst.

At M ¹for-CF ₃and M ²when for fluorine, by carboxylic acid (47) for initial substance, carry out synthetic compound (1M) according to described method.

Generate the example of the method for the concatenating group (S ≠ singly-bound) in compound (1) for such as shown in following flow process.In described flow process, MSG ¹for having any monovalent organic radical of at least one ring.Compound (1N) ~ compound (1Q) is equivalent to compound (1).

(2)-(CH ₂) _gthe generation of-O-

Under salt of wormwood etc. exists, the compound (49) synthesized with all perception methods is made to react with compound (30) and obtain compound (50).With reductive agents such as lithium aluminium hydride, compound (50) reduction is obtained compound (51).Compound (1N) is obtained by making compound (51) and carboxylic acid (41) dehydrating condensation.

(3)-(CH ₂) _gthe generation of-CH=CH-

With the alkali of tertiary butyl alcohol potassium and so on, the phosphonium salt synthesized with all perception methods (52) processed and produce phosphorus ylide, making this phosphorus ylide and aldehyde (32) react and obtain compound (53).Compound (1O) is obtained by making compound (53) and carboxylic acid (41) dehydrating condensation.

(4) generation of-CH=CH-

By under the existence of salt of wormwood etc., aldehyde (54), acid anhydrides (55) and the carboxylic acid sodium (56) of synthesizing with all perception methods is made to carry out reacting and obtain compound (1P).

(5)-(CH ₂) _g-CH ₂cH ₂-generation

Synthol (57) is carried out by compound (53) being carried out hydrogenation under the existence of the catalyzer of palladium carbon and so on.By making described alcohol and carboxylic acid (41) dehydrating condensation and obtaining compound (1Q).

(6) base (P-2) and base (P-3)

Polymerizability base is that in the compound of the vinyloxy group (P-2) be substituted, singly-bound generates as follows.Make HO-MGS ¹(30) react under salt of wormwood exists with the bromine ethene be substituted, obtain the compound with the vinyloxy group be substituted.Polymerizability base is in the compound of the allyloxy (P-3) be substituted, and singly-bound generates with Williamson synthesis (Williamsonsynthesis).That is, HO-MGS is passed through ¹(30) sodium salt and the reaction of bromopropylene be substituted and obtain the compound with the allyloxy be substituted.

3. Polymerizable composition

At least one of Polymerizable composition inclusion compound (1) is as the first composition.The composition of composition can be only the first composition.Composition also can comprise the second composition, the 3rd composition etc.The kind of the second composition etc. depends on kind as the polymkeric substance of target or purposes.Described Polymerizable composition still can comprise other polymerizable compounds different from compound (1) as the second composition.The preference of other polymerizable compounds is: acrylate, methacrylic ester, vinyl compound, ethyleneoxy compounds, propenyl ether, oxyethane (oxirane, trimethylene oxide) or vinyl ketone.More preferably example is: have the compound of at least one acryloxy or have the compound of at least one methacryloxy.More preferably the compound with acryloxy and methacryloxy is also comprised in example.

The additional example of other polymerizable compounds is: compound (M-1) ~ (M-12).In compound (M-1) ~ (M-12), R ²⁵, R ²⁶and R ²⁷independent is hydrogen or methyl; U, x and y are independently 0 or 1; V and w is independently 1 ~ 10; L ²¹, L ²², L ²³, L ²⁴, L ²⁵and L ²⁶independent is hydrogen or fluorine.

When the second composition of Polymerizable composition is the polymerizable compound with mesomorphic phase, makes it carry out being polymerized by the orientation controlling liquid crystal molecule and generate optically anisotropic body.Described optically anisotropic body can be used for phase retardation film, polarization element, rotatory polarization element, elliptical polarized light element, anti-reflective film, choice reflective film, colorimetric compensation film, compensation film for angular field of view etc.For the object of the physical property of adjustment optically anisotropic body, also the additives such as polymerization starter can be made an addition in Polymerizable composition.

Polymerizable composition also can comprise liquid-crystal composition as the second composition.For the purpose of the liquid crystal display device for PS-TN, PS-IPS, PS-FFS, PSA-VA, PSA-OCB isotype, the preferred inclusion compound of described composition (1) as composition A, and also comprises the compound be selected from composition B as follows, composition C and components D.Composition B is compound (2) ~ (4).Composition C is compound (5) ~ (7).Components D is compound (8).When preparing this kind of composition, consider the size etc. of dielectric anisotropy, be preferably selection component B, composition C and components D.Described composition also can comprise other liquid crystal compounds differing from composition B, composition C and components D.(namely the composition of suitable selection component has high ceiling temperature, low lower limit temperature, little viscosity, suitable optical anisotropy, large optical anisotropic or little optical anisotropy), large dielectric anisotropy, and suitable elastic constant (that is, large elastic constant or small constant).

Polymerizable composition is prepared by adding compound (1) in liquid-crystal composition.In this kind of composition, based on the weight of liquid-crystal composition, compound (1) the i.e. addition of composition A is in 0.05 % by weight ~ 20 % by weight scope.Preferred addition is in 0.1 % by weight ~ 10 % by weight scope.Most preferred addition is in 0.2 % by weight ~ 1 % by weight scope.Also other polymerizable compounds that at least one differs from compound (1) can also be added.Now compound (1) and the total addition of other polymerizable compounds are preferably in described scope.Suitable selection other polymerizable compound and the physical property of polymkeric substance that generates of adjustable.The example of other polymerizable compounds as aforementioned be acrylate, methacrylic ester etc.Also inclusion compound (M-1) ~ (M-12) in described example.

The compound of composition B to be two terminal group be alkyl etc.The preference of composition B can lift compound (2-1) ~ (2-11), compound (3-1) ~ (3-19) and compound (4-1) ~ (4-7).In the compound of composition B, R ¹¹and R ¹²definition identical with formula (2) ~ (4) recorded in item 12.

Composition B due to the absolute value of dielectric anisotropy little, so be close to neutral compound.Compound (2) mainly has adjustment viscosity or adjusts optically anisotropic effect.Compound (3) and compound (4) have by improving ceiling temperature and expand the effect of nematic temperature range or adjust optically anisotropic effect.

The content increasing composition B then composition viscosity diminishes, but dielectric anisotropy diminishes.As long as therefore meet the required value of the threshold voltage of element, then content is preferably many.Therefore, during preparation PS-IPS, PSA-VA isotype composition, based on the weight of liquid-crystal composition, composition B content preferably more than 30 % by weight, more preferably more than 40 % by weight.

Composition C has halogen at right end or contains fluorine-based compound.The preference of composition C can lift compound (5-1) ~ (5-16), compound (6-1) ~ (6-113) and compound (7-1) ~ (7-57).In the compound of composition C, R ¹³and X ¹¹definition identical with formula (5) ~ (7) recorded in item 13.

Composition C due to dielectric anisotropy be just, excellent to the stability of heat, light etc., so for the preparation of the composition of PS-IPS, PS-FFS, PSA-OCB isotype.Based on the weight of liquid-crystal composition, the content of composition C is adapted in the scope of 1 % by weight ~ 99 % by weight, preferably in the scope of 10 % by weight ~ 97 % by weight, more preferably in the scope of 40 % by weight ~ 95 % by weight.When composition C is made an addition to dielectric anisotropy is negative composition, based on the weight of liquid-crystal composition, composition C content is preferably below 30 % by weight.By added ingredients C, the elastic constant of adjustable composition, and the voltage-transmittance curve of adjustment element.

The compound (8) of components D to be right terminal group be-C ≡ N or-C ≡ C-C ≡ N.The preference of components D can lift compound (8-1) ~ (8-64).In the compound of components D, R ¹⁴and X ¹²definition identical with the formula (8) recorded in item 14.

Components D due to dielectric anisotropy be just, and its value is large, so mainly for the preparation of the situation of PS-TN isotype composition.By adding described components D, the dielectric anisotropy of composition can be increased.Components D has temperature range, the adjustment viscosity of expansion mesomorphic phase or adjusts optically anisotropic effect.Components D also can be used for the voltage-transmittance curve adjusting element.

During the composition of preparation PS-TN isotype, based on the weight of liquid-crystal composition, the content of components D should in the scope of 1 % by weight ~ 99 % by weight, preferably in the scope of 10 % by weight ~ 97 % by weight, more preferably in the scope of 40 % by weight ~ 95 % by weight.When components D to be made an addition to dielectric anisotropy be in negative composition, based on the weight of liquid-crystal composition, the content of components D is preferably less than 30 % by weight.By added ingredients D, the elastic constant of adjustable composition, and the voltage-transmittance curve of adjustment element.

The preparation of Polymerizable composition can utilize and the methods such as required composition dissolves at temperatures greater than room temperature are carried out.According to purposes, also additive can be added in the composition.The example of additive is: optically active compound, antioxidant, UV light absorber, photostabilizer, thermo-stabilizer, defoamer, polymerization starter, polymerization retarder etc.This kind of additive is well known to those skilled in the art, and is recorded in document.

Optically active compound has makes liquid crystal molecule produce spirane structure to give the effect of required torsion(al)angle and anti-non-return torsion.By adding optically active compound adjustable screw pitch.In order to adjust the temperature dependency of screw pitch, also two or more optically active compounds can be added.The preference of optically active compound can lift following compound (Op-1) ~ (Op-18).In compound (Op-18), ring J is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, and R ²⁸for the alkyl of carbon number 1 ~ 10.

Antioxidant can effectively maintain large voltage retention.The preference of antioxidant can lift following compound (AO-1) and (AO-2), easily this (IRGANOX) 415 of fine jade promise, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX3114 and IRGANOX1098 (trade(brand)name; BASF (BASF) company produces).UV light absorber can effectively prevent ceiling temperature from declining.The preference of UV light absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc., and concrete example can be lifted: following compound (AO-3) and (AO-4), refined (TINUVIN) 329 of Supreme Being slave, TINUVINP, TINUVIN326, TINUVIN234, TINUVIN213, TINUVIN400, TINUVIN328, TINUVIN99-2 (trade(brand)name; BASF AG produces) and Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane (DABCO).For maintaining large voltage retention, be preferably the photostabilizers such as bulky amine.The preference of photostabilizer can lift following compound (AO-5) and (AO-6), TINUVIN144, TINUVIN765 and TINUVIN770DF (trade(brand)name; BASF AG produces).Again, thermo-stabilizer also can effectively maintain large voltage retention, and preference can lift easy fine jade Floex (IRGAFOS) 168 (trade(brand)name; BASF AG produces).Defoamer can effectively prevent from bubbling.The preference of defoamer is dimethylsilicone oil, methylphenylsilicone oil etc.

In compound (AO-1), R ²⁹for the alkyl of carbon number 1 ~ 20, the alkoxyl group ,-COOR of carbon number 1 ~ 20 ³²or-CH ₂cH ₂cOOR ³², R herein ³²for the alkyl of carbon number 1 ~ 20.In compound (AO-2) and (AO-5), R ³⁰for the alkyl of carbon number 1 ~ 20.In compound (AO-5), R ³¹for hydrogen, methyl or O (oxyradical), ring K and ring L are Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, x is 0,1 or 2.

4. liquid crystal complex body

Compound (1) has high polymerisation reactivity, high conversion and the high-dissolvability in liquid-crystal composition.The Polymerizable composition polymerization of inclusion compound (1) and liquid-crystal composition is made namely to generate liquid crystal complex body.Compound (1) generates polymkeric substance by polymerization in liquid-crystal composition.Described polymkeric substance has the effect making liquid crystal molecule produce pre-dumping.Preferably be polymerized under Polymerizable composition demonstrates the temperature of mesomorphic phase.Polymerization is undertaken by heat, light etc.Preferred reaction is photopolymerization.In order to prevent producing thermopolymerization simultaneously, preferably below 100 DEG C, carry out photopolymerization.Also can be polymerized under the state applying electric field or magnetic field.

The polymerisation reactivity of adjustable compound (1) and transformation efficiency.Compound (1) is suitable for radical polymerization.Make temperature of reaction optimizing can reduce the amount of Bottom Compound (1).Compound (1) is rapid polymerization by interpolation polymerization starter.The example of optical free radical polymerization starter is: the moral of Ciba (CibaSpecialtyChemicals) (stock) TPO firmly in (Darocur) series, 1173 and 4265, Yi Lujia (Irgacure) series in 184,369,500,651,784,819,907,1300,1700,1800,1850 and 2959.

The additional example of optical free radical polymerization starter is: 4-p-methoxy-phenyl-2, two (trichloromethyl) triazine of 4-, 2-(4-butyl phenyl ether vinyl)-5-trichloromethyl-1, 3, 4-oxadiazole, 9-phenylacridine, 9, 10-phenonaphthazine, benzophenone/michaelis ketone mixture, six aryl bisglyoxaline/mercaptobenzimidazole mixtures, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, benzyl dimethyl ketal, 2-methyl isophthalic acid-[4-(methylsulfany) phenyl]-2-morpholinopropane-1-ketone, 2, 4-diethyl xanthone/ESCAROL 507 mixtures of methyl esters, benzophenone/methyl triethanol amine mixt.

By add optical free radical polymerization starter in Polymerizable composition after, under the state applying electric field, irradiation ultraviolet radiation is polymerized.But the degradation production of unreacted polymerization starter or polymerization starter may make the displays such as element generation image retention bad.In order to prevent described display bad, also photopolymerization can be carried out under the state of not adding polymerization starter.The wavelength of the light irradiated is preferably in the scope of 150nm ~ 500nm.Preferred wavelength is in the scope of 250nm ~ 450nm, and most preferred wavelength is in the scope of 300nm ~ 400nm.

When preserving polymerizable compound, for preventing polymerization, also polymerization retarder can be added.The state that polymerizable compound Chang Yiwei removes polymerization retarder adds composition.The example of polymerization retarder is the hydroquinone derivative such as Resorcinol, methyl hydroquinone, 4-tert-butyl catechol, 4-methoxyphenol, thiodiphenylamine (phenothiazine) etc.

5. liquid crystal display device

The effect of the polymkeric substance in liquid crystal display device is explained as follows.Polymerizable composition is the mixture of liquid crystal compounds, polymerizable compound etc.By applying electric field, then liquid crystal molecule orientation on the direction of electric field to described composition.According to described orientation, polymerizable compound is orientation also.To composition irradiation ultraviolet radiation, under the state maintaining orientation, polymerizable compound is polymerized, forms tridimensional network.When removing electric field, also maintain the orientation of polymkeric substance.Liquid crystal molecule carries out stabilization because of the effect of described polymkeric substance with the state of orientation on the direction of electric field.Therefore, the time of response of element shortens.

The polymerization of Polymerizable composition is preferably carried out in display element.Wherein one such as lower described in.Prepare the display element comprising two pieces of glass substrates, described glass substrate possesses transparency electrode and alignment films.Preparation take compound (1), liquid-crystal composition, additive etc. as the Polymerizable composition of composition.Described composition is injected display element.Be polymerized while apply electric field one side irradiation ultraviolet radiation to described display element to make compound (1).Liquid crystal complex body is generated by described polymerization.Utilize described method, can easily make the liquid crystal display device with liquid crystal complex body.In described method, also can omit the friction treatment of alignment films.In addition, also can adopt and make liquid crystal molecule carry out the method for stabilization under without the state of electric field.

When the weight based on liquid-crystal composition, when the addition of polymkeric substance is in the scope of 0.1 % by weight ~ 2 % by weight, make the liquid crystal display device of PSA pattern.The element of PSA pattern can active matrix (AM), passive matrix (passivematrix, PM) and so on type of drive drive.This kind of element can be applicable to arbitrary type of reflection-type, infiltration type, semi-transmission type.By increasing the addition of polymkeric substance, the element of polymer dispersion pattern also can be made.

[embodiment]

Come by the following examples to elaborate further to the present invention.The present invention is not by the restriction of these embodiments.

6. the embodiment of compound (1)

Compound (1) is synthesized by program shown in embodiment 1 grade.Synthesized compound is identified by methods such as nucleus magnetic resonance (NMR) analyses.The physical property of compound utilizes the following method recorded to measure.

NMR analyzes

Determinator uses DRX-500 (this guest of Brooker Baier (BrukerBioSpin) (stock) Inc.). ¹h-NMR makes sample be dissolved in CDCl in measuring ₃deng in deuterated solvents, at room temperature measure with the condition of 500MHz, cumulative number 16 times.Take tetramethylsilane as internal standard. ¹⁹during F-NMR measures, use CFCl ₃for internal standard, carry out for 24 times with cumulative number.In the explanation of NMR (Nuclear Magnetic Resonance) spectrum, s refers to unimodal, and d refers to doublet, t refers to triplet, and q refers to quartet, and quin refers to quintet (quintet), sex refers to sextet (sextet), and m refers to multiplet (multiplet), br finger beam peak (broad).

High performance liquid chromatography (HPLC) is analyzed

Pu Luominsi (the Prominence) (LC-20AD that determinator uses Shimadzu Seisakusho Ltd. to manufacture; SPD-20A).Tubing string uses YMC YMC-Parker (YMC-Pack) ODS-A (length 150mm, internal diameter 4.6mm, particle diameter 5 μm).Lye is suitably mixed with water by acetonitrile to use.Detector suitably uses ultraviolet (UV) detector, specific refractory power (RI) detector, corona detection device (Coronadetector) etc.When using UV detector, determined wavelength is set to 254nm.Sample dissolution, in acetonitrile, is prepared into the solution of 0.1 % by weight, is imported in sample chamber by described solution 1 μ L.The C-R7Aplus that recording gauge uses Shimadzu Seisakusho Ltd. to manufacture.

UV, visible light spectrum analysis

Method agate Spike (PharmaSpec) UV-1700 that determinator uses Shimadzu Seisakusho Ltd. to manufacture.Determined wavelength is set to 190 ~ 700nm.Sample dissolution, in acetonitrile, is prepared into the solution of 0.01mmol/L, adds in quartz cell (path length is 1cm) and measures.

Measure sample

When measuring phase structure and transformation temperature (brocken spectrum, fusing point, polymerization initiation temperature etc.), compound itself is used as sample.When measuring the physical property such as nematic phase ceiling temperature, viscosity, optical anisotropy, dielectric anisotropy, the mixture of compound and mother liquor crystalline substance is used as sample.

Measuring method

The mensuration of physical property is carried out with following method.These methods are the middle method recorded of JEITA standard (JEITAED-2521B) that electronic information technology industry association of Corporation (JEITA) review is formulated mostly, or the method for being modified.On the TN element measured, thin film transistor (TFT) is not installed.

(1) phase structure

Possessing hot plate (plum Teller (Mettler) company of melting point apparatus of polarizing microscope, FP-52 type warm table) on place sample, while carry out heating with the speed of 3 DEG C/min while utilize polarizing microscope to observe phase state and change thereof, determine the kind of phase.

(2) transition temperature (DEG C)

The high sensitivity differential scanning calorimetry X-DSC7000 that scanning calorimeter Dai Meng get (Diamond) the DSC system using perkin elmer (PerkinElmer) company to manufacture or SSI nanotechnology (SSINanotechnology) company manufacture measures.Sample is carried out intensification cooling with the speed of 3 DEG C/min, is obtained the endothermic peak of the phase change of adjoint sample or the starting point of heating peak value by extrapolation, determine transition temperature.Fusing point, the polymerization initiation temperature of compound also use described device to measure.Sometimes be that the temperature of the mesomorphic phase such as smectic phase, nematic phase is referred to as " lower limit temperature of mesomorphic phase " from solid transition by compound.Sometimes be that the temperature of liquid is referred to as " brocken spectrum " from liquid crystal phase transition by compound.

Crystallization is expressed as C.When being distinguished the kind of crystallization, be expressed as C ₁, C ₂.Smectic phase is expressed as S, and nematic phase is expressed as N.In smectic phase, when being added stratose A phase, stratose B phase, stratose C phase or stratose F to distinguish, be expressed as S _a, S _b, S _cor S _f.Liquid (isotropy) is expressed as I.Transition temperature is such as expressed as " C50.0N100.0I ".This represent, certainly crystallize to that nematic transition temperature is 50.0 DEG C, from nematic phase to the transition temperature of liquid be 100.0 DEG C.

(3) nematic ceiling temperature (T _nIor NI; DEG C)

Sample placed by the hot plate of melting point apparatus possessing polarizing microscope, heats with the speed of 1 DEG C/min.Measure the temperature of a part when nematic phase is changed to isotropic liquid of sample.Sometimes by nematic phase ceiling temperature referred to as " ceiling temperature ".When sample is the mixture of compound and mother liquor crystalline substance, with mark T _nIrepresent.When sample is the mixture of compound and composition B, C, D or E, represent with mark NI.

(4) nematic lower limit temperature (T _c; DEG C)

After 10 days, mesomorphic phase is observed by having the keeping in the refrigerator of 0 DEG C ,-10 DEG C ,-20 DEG C ,-30 DEG C and-40 DEG C of nematic sample.Such as, when sample is nematic state at-20 DEG C, and when being changed to crystallization or smectic phase at-30 DEG C, by T _cji Zai Wei≤-20 DEG C.Sometimes by nematic lower limit temperature referred to as " lower limit temperature ".

(5) viscosity (volume viscosity; η; Measure at 20 DEG C; MPas)

The E type rotational viscosimeter using Tokyo gauge limited-liability company to manufacture measures.

(6) optical anisotropy (refractive anisotrop; Measure at 25 DEG C; Δ n)

Use the light of wavelength 589nm, utilize the Abbérefractometer installing Polarizer on ocular lens to measure.By the surface of headprism after a direction friction, sample is dripped on headprism.Specific refractory power (n ∥) be the direction of polarisation and the direction of friction parallel time measure.Specific refractory power (n ⊥) be the direction of polarisation and the direction of friction vertical time measure.The value of optical anisotropy (Δ n) calculates according to the formula of Δ n=n ∥-n ⊥.

(7) ratio resistance (ρ; Measure at 25 DEG C; Ω cm)

Sample 1.0mL is injected in the container possessing electrode.Volts DS (10V) is applied to described container, measures the galvanic current after 10 seconds.Ratio resistance is calculated by following formula.(ratio resistance)={ (voltage) × (electric capacity of container) }/{ (galvanic current) × (specific inductivity of vacuum) }.

(8) voltage retention (VHR-1; Measure at 25 DEG C; %)

TN element for measuring has alignment film of polyimide, and the interval of two pieces of glass substrates (intercellular space) is 5 μm.Described element, after putting into sample, utilizes and seals with UV cured caking agent.Apply pulsed voltage (5V, 60 microseconds) to described element to charge.Utilize high speed potentiometer between 16.7 milliseconds, measure the voltage of decaying, obtain the area A between voltage curve in unit period and transverse axis.Area B is area when not decaying.Voltage retention represents with the per-cent of area A relative to area B.

(9) voltage retention (VHR-2; Measure at 80 DEG C; %)

Except replacing 25 DEG C and measure at 80 DEG C, to measure voltage retention with described identical program.The result of gained is represented with the mark of VHR-2

Be positive sample and dielectric anisotropy for dielectric anisotropy be negative sample, the assay method of physical property is sometimes different.Dielectric anisotropy is that the assay method of timing is recorded in item (10) ~ (14).

(10) viscosity (rotary viscosity; γ 1; Measure at 25 DEG C; MPas)

The method recorded in " molecular crystal and liquid crystal (MolecularCrystalsandLiquidCrystals) " the 259th phase the 37th page (nineteen ninety-five) according to people such as the modern wells (M.Imai) of M. measures.Be 0 degree and two pieces of glass substrate spacings (intercellular space) are put into sample in the TN element of 5 μm at torsion(al)angle.With the jump of 0.5V, interim applying voltage is come to described element within the scope of 16V ~ 19.5V.Do not apply voltage after 0.2 second, only to apply 1 square wave (square topped pulse; 0.2 second) repeatedly apply with the condition not applying voltage (2 seconds).The peak point current (peakcurrent) of the transient current (transientcurrent) produced because of described applying and time to peak (peaktime) are measured.The value of rotary viscosity is obtained according to the calculating formula (8) of the paper the 40th page of the people such as these measured values and the modern well of M..The value of the dielectric anisotropy required for described calculating is the element of rotary viscosity after measured described in use, obtains with following described method.

(11) dielectric anisotropy (Δ ε; Measure at 25 DEG C)

Be 9 μm and torsion(al)angle at the interval (cell gap) of two pieces of glass substrates be put into sample in the TN element of 80 degree.Described element is applied sinusoidal wave (10V, 1kHz), within 2 seconds, measures the specific inductivity (ε ∥) of the long axis direction of liquid crystal molecule afterwards.Described element is applied sinusoidal wave (0.5V, 1kHz), within 2 seconds, measures the specific inductivity (ε ⊥) of the short-axis direction of liquid crystal molecule afterwards.The value of dielectric anisotropy calculates according to the formula of Δ ε=ε ∥-ε ⊥.

(12) elastic constant (K; Measure at 25 DEG C; PN)

Measure HP4284A type Inductance, Capacitance, Resistance (LCR) (LCR) meter using Yokogawa Hewlett-Packard (Yokogawa-Hewlett-Packard) limited-liability company to manufacture.Be put into sample in the horizontal alignment element of 20 μm two pieces of glass substrate spacings (intercellular space).0 volt ~ 20 volts electric charges are applied to described element, measures electrostatic capacitance and apply voltage.Use " liquid-crystal apparatus handbook " (Nikkan Kogyo Shimbun) the 75th page (2.98), formula (2.101) come the electrostatic capacitance (C) that matching (fitting) records and the value applying voltage (V), obtain K according to formula (2.99) ₁₁and K ₃₃value.Then, with the formula (3.18) of the 171st page and the K that just now obtained ₁₁and K ₃₃value calculating K ₂₂.Elastic constant K is expressed as the K obtained in the above described manner ₁₁, K ₂₂and K ₃₃mean value.

(13) threshold voltage (Vth; Measure at 25 DEG C; V)

Measure the LCD5100 type luminance meter using great Zhong electronics limited-liability company.Light source is halogen lamp.Two pieces of glass substrate spacings (intercellular space) be 0.45/ Δ n (μm), torsion(al)angle is put into sample in the TN element of the normal white mode (normallywhitemode) of 80 °.The voltage (32Hz, square wave) applied described element take 0.02V as jump, is increased to 10V from 0V stage.Now, from vertical direction to element irradiation, measure the light quantity through element.Making the transmitance when described light quantity reaches maximum is 100%, and when described light quantity is minimum, transmitance is the voltage-transmittance curve of 0%.Threshold voltage is that voltage when reaching 90% with transmitance represents.

(14) time of response (τ; Measure at 25 DEG C; Ms)

Measure the LCD5100 type luminance meter using great Zhong electronics limited-liability company.Light source is halogen lamp.Low-pass filter (Low-passfilter) is set to 5kHz.Two pieces of glass substrate spacings (intercellular space) be 5.0 μm, torsion(al)angle is put into sample in the TN element of the normal white mode (normallywhitemode) of 80 °.Square wave (60Hz, 5V, 0.5 second) is applied to described element.Now from vertical direction to element irradiation, measure the light quantity through element.Be considered as transmitance 100% when described light quantity reaches maximum, be considered as transmitance 0% when described light quantity is minimum.Rise time (τ r:risetime; Millisecond) rate that is through is changed to time needed for 10% from 90%.Fall time (τ f:falltime; Millisecond) rate that is through is changed to time needed for 90% from 10%.Time of response be expressed as rise time of obtaining in the above described manner and fall time and.

[embodiment 1]

The synthesis of compound (1-3-12)

1st step:

By 4-bromophenol (T-1) (50.0g, 289.01mmol; Tokyo changes into Industries, Inc) and toluene (250ml) solution of diisopropyl ethyl amine (56.03g, 433.5mmol) carry out ice bath cooling, drip chloromethyl methyl ether (34.9g, 433.51mmol).Stir after 3 hours, reaction mixture is injected saturated aqueous ammonium chloride (200ml), utilize ethyl acetate to extract.By extraction liquid with water (300ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/heptane=2/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-2) (57.6g, 265.1mol, 91.7%).

2nd step:

Tetrahydrofuran (THF) (THF) (290ml) solution of the compound (T-2) (57.6g, 265.1) 1st step obtained is cooled to-40 DEG C, drips n-BuLi (1.59M, 200.3ml, 318.4mmol).Stir at-40 DEG C after 2 hours, drip trimethoxy-boron (35.85g, 344.97mmol).Stirred at ambient temperature 8 hours, injects saturated aqueous ammonium chloride (300ml), with extraction into ethyl acetate by reaction mixture.By extraction liquid with water (300ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate, and obtain compound (T-3) (32.7g, 179.69mol, 67.7%).

3rd step:

With bromo-2, the 5-chlorophenesic acid (T-4) of ice bath cooling 4-(200.0g, 826.80mmol; Tokyo changes into Industries, Inc) THF (1000ml) solution, 55% sodium hydride (43.3g, 992.16mmol) is added points for 5 times, stirs 1 hour.Then chloromethyl methyl ether (86.5g, 1074.84mmol) is dripped.Stir and reaction mixture is injected saturated aqueous ammonium chloride (1000ml) after 3 hours, extract with toluene.By extraction liquid with water (200ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/heptane=2/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-5) (235.8g, 824.54mol, 99.7%).

4th step:

By tetrahydrofuran solution (1.3M, 322.8ml, 419.65mmol of isopropylmagnesium chloride lithium chloride complex compound, aldrich (Aldrich) company produces) be cooled to 0 DEG C, drip THF (500ml) solution of compound (T-5) (100.0g, 349.71mol) that the 3rd step obtains.Stir at 40 DEG C after 2 hours, add cupric iodide (3.3g, 17.49mmol), then drip methyl iodide (26.1ml, 419.65mmol).At room temperature stir 8 hours, reaction mixture is injected saturated aqueous ammonium chloride (300ml), with extraction into ethyl acetate.By extraction liquid with water (300ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/heptane=2/1 (volume ratio)) that residue is carried out purifying, and then obtain compound (T-6) (64.7g, 292.36mol, 83.6%) by recrystallize (methyl alcohol).

5th step:

By compound (the T-6) (30.0g that the 4th step obtains, 135.7mmol), compound (the T-3) (59.3g that 2nd step obtains, 325.67mmol), acid chloride (II) (0.152g, 0.68mmol), 2-dicyclohexyl phosphino--2', 6'-dimethoxy-biphenyl (0.557g, 1.36mmol), sodium phosphate dodecahydrate (154.74g, 407.09mmol), Tetrabutyl amonium bromide (TBAB) (17.5g, 54.28mmol), toluene (200ml), Virahol (200ml) and water (200ml) mixing, carry out 16 hours reflux.Reaction mixture is placed after being cooled to room temperature and filter, by filtrate with water (300ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/ethyl acetate=9/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-7) (57.0g, 134.28mmol, 98.9%).

6th step:

THF at compound (T-7) (57.0g, 134.28mmol) that the 5th step obtains: add 2N hydrochloric acid (268.56ml, 537.12mmol) in ethanol=1:1 mixing solutions (300ml), stirs 3 hours at 70 DEG C.Reaction mixture is placed after being cooled to room temperature, inject water (500ml), utilize ethyl acetate (500ml) to extract.Extraction liquid is cleaned 5 times with water (100ml), with anhydrous magnesium sulfate drying, under reduced pressure concentrates, and obtain compound (T-8) (31.8g, 108.78mmol, 81.0%).

7th step:

Compound (T-8) (31.8g, 108.78mmol) that 6th step is obtained, methacrylic acid (32.8g, 380.74mmol) and N, N-dimethyl-4-aminopyridine (DMAP; 13.29g, 108.78mmol) be dissolved in toluene (500ml), cool with ice bath.Marginally add dicyclohexylcarbodiimide (DCC with solid state at every turn; 78.55g, 380.74mmol) after, at room temperature stir 8 hours.Reaction mixture is filtered by diatomite, utilize column chromatography (lye: toluene/ethyl acetate=19/1 (volume ratio)) by filtrate purifying, carry out recrystallize (heptane/ethyl acetate=1/1 (volume ratio)) again, obtain compound (1-3-12) (28.2g, 56.74mmol, 52.2%) thus.

Fusing point: 120.7 DEG C

¹H-NMR(CDCl ₃；δppm):7.48(d,2H),7.41(d,2H),7.32(s,1H),7.19(d,2H),7.16(d,2H),7.08(s,1H),6.38(s,1H),6.36(s,1H),6.17(s,1H),5.77(s,2H),5.63(s,1H),2.33(s,3H),2.09(s,3H),2.08(s,3H),1.92(s,3H).

[embodiment 2]

The synthesis of compound (1-3-1)

1st step:

With ice bath cooling 2,5-chlorophenesic acid (T-9) (50.0g, 306.75mmol; Tokyo changes into Industries, Inc) THF (500ml) solution, 55% sodium hydride (16.06g, 368.10mmol) is added points for 3 times, stirs 1 hour.Then chloromethyl methyl ether (29.6g, 368.10mmol) is dripped.Stir and reaction mixture is injected saturated aqueous ammonium chloride (500ml) after 3 hours, extract with toluene.By extraction liquid with water (200ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/heptane=2/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-10) (63.0g, 303.96mol, 99.1%).

2nd step:

By compound (the T-10) (23.0g that the 1st step obtains, 111.08mmol), compound (the T-3) (44.3g that embodiment 1 the 2nd step obtains, 233.27mmol), acid chloride (II) (0.249g, 1.11mmol), 2-dicyclohexyl phosphino--2', 6'-dimethoxy-biphenyl (0.912g, 2.22mmol), sodium phosphate dodecahydrate (126.68g, 333.25mmol), Tetrabutyl amonium bromide (TBAB) (17.9g, 55.54mmol), toluene (200ml), Virahol (200ml) and water (200ml) mixing, carry out 16 hours reflux.Reaction mixture is placed after being cooled to room temperature and filter, by filtrate with water (300ml) and saturated aqueous common salt (200ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/ethyl acetate=9/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-11) (35.3g, 85.83mmol, 77.3%).

3rd step:

The THF of compound (T-11) (35.3g, 134.28mmol) of obtaining in the 2nd step: in ethanol=1:1 mixing solutions (300ml), add 2N hydrochloric acid (268.56ml, 537.12mmol), stir 3 hours at 70 DEG C.Reaction mixture is placed after being cooled to room temperature, inject water (500ml), extract with ethyl acetate (500ml).Extraction liquid is cleaned 5 times with water (100ml), with anhydrous magnesium sulfate drying, under reduced pressure concentrates, and obtain compound (T-12) (23.9g, 85.88mmol, 99.9%).

4th step:

Compound (T-12) (23.9g, 85.88mmol) that 3rd step is obtained, methacrylic acid (29.57g, 343.51mmol) and N, N-dimethyl-4-aminopyridine (DMAP; 10.49g, 85.88mmol) be dissolved in toluene (500ml), cool with ice bath.Marginally add dicyclohexylcarbodiimide (DCC with solid state at every turn; 70.88g, 343.51mmol) after, at room temperature stir 8 hours.Reaction mixture is filtered by diatomite, with column chromatography (lye: toluene/ethyl acetate=19/1 (volume ratio)), filtrate is carried out purifying, carry out recrystallize (heptane/ethyl acetate=1/1 (volume ratio)) again, and obtain compound (1-3-1) (22.7g, 47.00mmol, 54.7%).

Fusing point: 114.4 DEG C

¹H-NMR(CDCl ₃；δppm):7.65(d,2H),7.60-7.45(m,4H),7.40(s,1H),7.21(d,2H),7.16(d,2H),6.38(s,1H),6.37(s,1H),6.20(s,1H),5.78(s,2H),5.66(s,1H),2.08(s,6H),1.94(s,3H).

[embodiment 3]

The synthesis of compound (1-3-53)

1st step:

By 1, 4-bis-bromo-2, 5-dimethoxy benzene (T-13) (25.0g, 84.47mmol, Tokyo changes into industry), 4-methoxyphenyl-boronic acid (T-14) (28.2g, 185.84mmol, Tokyo changes into industry), two (two-tertiary butyl (4-dimethylaminophenyl) phosphine) dichloro palladium (II) (0.30g, 0.42mmol), Trisodium phosphate dodecahydrate (96.33g, 253.42mmol), Tetrabutyl amonium bromide (TBAB) (5.45g, 16.89mmol), toluene (100ml), Virahol (100ml) and water (100ml) mixing, reflux 5 hours.Reaction mixture is placed after being cooled to room temperature and filter, by filtrate with water (200ml) and saturated aqueous common salt (100ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/ethyl acetate=9/1 (volume ratio)) that residue is carried out purifying, obtain compound (T-15) (27.9g, 84.47mmol, 94.3%).

2nd step:

Compound (T-15) (27.9g, 5.80mmol) that 1st step obtains is dissolved in methylene dichloride (200ml), is cooled to-60 DEG C.Drip boron tribromide (99.7g, 398.11mmol) in described solution after, stir 1 hour at-60 DEG C, be warming up to room temperature afterwards, stir 8 hours.Reaction mixture is injected water (500ml), extract with ethyl acetate (200ml).By extraction liquid with water (100ml, 3 times) and saturated aqueous common salt (100ml) cleaning after, with anhydrous magnesium sulfate drying, under reduced pressure concentrate, and obtain compound (T-16) (23.0g, 78.15mmol, 98.1%).

3rd step:

Compound (T-16) (7.8g, 26.50mmol) that 2nd step is obtained, methacrylic acid (9.13g, 106.01mmol) and N, N-dimethyl-4-aminopyridine (DMAP; 1.30g, 10.60mmol) be dissolved in toluene (100ml), cool with ice bath.Marginally add dicyclohexylcarbodiimide (DCC with solid state at every turn; 24.06g, 114.62mmol) after, at room temperature stir 8 hours.Reaction mixture is filtered by diatomite, with column chromatography (lye: toluene/ethyl acetate=19/1 (volume ratio)), filtrate is purified, carry out recrystallize (heptane/ethyl acetate=1/1 (volume ratio)) again, and obtain compound (1-3-53) (0.81g, 1.42mmol, 5.34%).

Fusing point: 212.7 DEG C

¹H-NMR(CDCl ₃；δppm):7.49(d,4H),7.26(d,4H),7.16(d,2H),6.36(s,2H),6.19(s,2H),5.77(s,2H),5.66(s,2H),2.07(s,6H),1.93(s,6H).

[embodiment 4]

The synthesis of compound (1-3-56)

1st step:

At 4-bromophenol (T-1) (507.25g, 2932.0mmol; Tokyo changes into Industries, Inc) and tosic acid pyridine (50.72g, 201.85mmol) methylene dichloride (2500ml) solution in, drip 3,4-dihydro-2H-pyrans (69.71g, 5864.0mmol).Stir and reaction mixture is injected saturated sodium bicarbonate aqueous solution (2000ml) after 4 hours, with extraction into ethyl acetate.By extraction liquid with water (3000ml) and saturated aqueous common salt (2000ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/heptane=2/1 (volume ratio)) by residue purifying, obtain compound (T-17) (723.7g, 2815.0mmol, 96.1%).

2nd step:

THF (3600ml) solution of compound (T-17) (723.7g, 2815.0mmol) of the 1st step being obtained is cooled to-40 DEG C, drips n-BuLi (1.59M, 2290ml, 3659.0mmol).Stir after 2 hours at-40 DEG C, drip three isopropoxy boron (688.16g, 3659.0mmol).At room temperature stir 8 hours, reaction mixture is injected saturated aqueous ammonium chloride (4000ml), with extraction into ethyl acetate.By extraction liquid with water (3000ml) and saturated aqueous common salt (2000ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Recrystallize (heptane) is carried out to residue and obtains compound (T-18) (203.12g, 914.77mmol, 32.5%).

3rd step:

Toluene (360ml) solution of tert-butylamine (179.59g, 2455.4mmol) is cooled to-30 DEG C, drips bromine (143.88g, 900.31mmol).After being cooled to-70 DEG C, drip the chloro-4-fluorophenol (T-19) (120g, 818.83mmol) of 3-.At room temperature stir 10 hours, reaction mixture is injected 1N hydrochloric acid (2000ml), clean with water (2000ml).By organic phase with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: heptane/ethyl acetate=5/1 (volume ratio)) by residue purifying, obtain compound (T-20) (105.17g, 466.52mmol, 57.0%).

4th step:

By compound (T-20) (105.17g, the 466.52mmol), potassiumphosphate (159.59g, 933.05mmol) and the N that obtain in the 3rd step, dinethylformamide (1000ml) mixes, after dripping bromotoluene (108.92g, 513.18mmol), stir 4 hours at 70 DEG C.Reaction mixture is filtered by diatomite, filtrate is injected water (1000ml), with extraction into ethyl acetate.Extraction liquid is cleaned 5 times with water (200ml), with anhydrous magnesium sulfate drying, concentrates in decompressionization.Utilize column chromatography (lye: toluene/heptane=1/1 (volume ratio)) by residue purifying, carry out recrystallize (ethanol) again, and obtain compound (T-21) (138.09g, 437.60mmol, 93.8%).

5th step:

Compound (T-21) (138.09g, 437.60mmol), benzyloxyphenylboronic acid (109.77g, 481.36mmol) that 4th step is obtained, tetrakis triphenylphosphine palladium (0) (1.01g, 0.88mmol), salt of wormwood (120.95g, 875.20mmol), Tetrabutyl amonium bromide (TBAB; 35.27g, 109.40mmol), toluene (700ml), Virahol (700ml) and water (300ml) mixing, carry out 16 hours reflux.Reaction mixture is placed after being cooled to room temperature and filter, by filtrate with water (900ml) and saturated aqueous common salt (600ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene/ethyl acetate=9/1 (volume ratio)) by residue purifying, obtain compound (T-22) (168.09g, 401.28mmol, 91.7%).

6th step:

Compound (T-18) (98.01g, 441.41mmol), acid chloride (II) (0.45g, 2.01mmol), 2-dicyclohexyl phosphino--2' that compound (T-22) (168.09g, 401.28mmol) of 5th step being obtained, the 2nd step obtain, 6'-dimethoxy-biphenyl (1.65g, 4.01mmol), sodium phosphate dodecahydrate (228.8g, 601.92mmol), Tetrabutyl amonium bromide (TBAB; 32.34g, 100.32mmol), toluene (840ml), Virahol (840ml) and water (840ml) mixing, carry out 16 hours reflux.Reaction mixture is placed after being cooled to room temperature and filter, by filtrate with water (900ml) and saturated aqueous common salt (600ml) cleaning, with anhydrous magnesium sulfate drying, under reduced pressure concentrate.Utilize column chromatography (lye: toluene) by residue purifying, and obtain compound (T-23) (218.91g, 390.44mmol, 97.3%).

7th step:

In Virahol (2200ml) solution of the 6th step acquisition compound (T-23) (218.91g, 390.44mmol), add palladium carbon (10.95g), add hydrogen, at room temperature stir 16 hours.Reaction mixture is filtered, utilize column chromatography (lye: toluene/ethyl acetate=2/1 (volume ratio)) by filtrate purifying, and obtain compound (T-24) (77.53g, 203.81mmol, 52.2%).

8th step:

Compound (T-24) (77.53g, 203.81mmol) that 7th step is obtained, methacrylic acid (26.32g, 305.72mmol) and N, N-dimethyl-4-aminopyridine (DMAP; 6.22g, 50.95mmol) be dissolved in methylene dichloride (780ml), cool with ice bath.Marginally add dicyclohexylcarbodiimide (DCC with solid state at every turn; 63.08g, 305.72mmol) after, at room temperature stir 8 hours.Reaction mixture is filtered by diatomite, utilize column chromatography (lye: toluene/ethyl acetate=19/1 (volume ratio)) by filtrate purifying, carry out recrystallize (heptane/ethyl acetate=1/1 (volume ratio)) again, and obtain compound (T-25) (32.32g, 62.57mmol, 30.7%).

9th step:

THF at compound (T-25) (32.32g, 62.57mmol) that the 8th step obtains: in ethanol=1:1 mixing solutions (300ml), add 2N hydrochloric acid (62.57ml, 125.14mmol), stir 3 hours at 70 DEG C.Reaction mixture is placed after being cooled to room temperature, inject water (500ml), extract with ethyl acetate (500ml).Extraction liquid is cleaned 5 times with water (100ml), with anhydrous magnesium sulfate drying, under reduced pressure concentrates, and obtain compound (T-26) (26.95g, 62.32mmol, 99.6%).

10th step:

Compound (T-26) (26.95g, 62.32mmol) that 9th step is obtained, vinylformic acid (6.74g, 93.48mmol) and N, N-dimethyl-4-aminopyridine (DMAP; 1.90g, 15.58mmol) be dissolved in methylene dichloride (300ml), cool with ice bath.Marginally add dicyclohexylcarbodiimide (DCC with solid state at every turn; 19.29g, 93.48mmol) after, at room temperature stir 8 hours.Reaction mixture is filtered by diatomite, utilize column chromatography (lye: toluene/ethyl acetate=19/1 (volume ratio)) by filtrate purifying, carry out recrystallize (heptane/ethyl acetate=1/1 (volume ratio)) again, and obtain compound (1-3-56) (29.5g, 60.64mmol, 97.3%).

Fusing point: 150.6 DEG C

¹H-NMR(CDCl ₃；δppm):7.63(dd,2H),7.48(m,2H),7.27(m,2H),7.24(m,2H),7.18(m,2H),6.63(dd,1H),6.38(s,1H),6.20(s,1H),6.05(dd,1H),5.78(s,2H),5.67(s,1H),2.08(s,3H),1.93(s,3H).

[embodiment 5]

Utilize the method shown in embodiment 1 ~ 4, use corresponding starting raw material to synthesize multiple compounds, confirm as target compound.

Compound (1-3-21)

Fusing point: 124.23 DEG C

¹H-NMR(CDCl ₃；δppm):7.63(dd,2H),7.47(d,2H),7.27(d,1H),7.24(d,1H),7.22(d,2H),7.18(d,2H),6.37(s,2H),6.20(s,1H),5.79(dd,2H),5.67(dd,2H),2.09(s,3H),2.08(s,3H),1.93(s,3H).

Compound (1-3-16)

Fusing point: 115.50 DEG C

¹H-NMR(CDCl ₃；δppm):7.48(d,2H),7.41(d,2H),7.32(s,1H),7.19(d,2H),7.16(d,2H),7.08(s,1H),6.38(s,1H),6.36(s,1H),6.17(s,1H),5.77(s,2H),5.63(s,1H),4,06(t,3H),2.09(s,3H),2.08(s,3H),1.92(s,3H),1.76(m,2H),1.45(m,2H),0.90(t,3H).

Compound (1-3-2)

Fusing point: 116.20 DEG C

¹H-NMR(CDCl ₃；δppm):7.65(d,2H),7.60(d,1H),7.47(t,2H),7.24(d,2H),7.22(d,2H),6.71(d,1H),6.68(d,1H),6.56(s,1H),6.52(s,1H),6.40(m,2H),6.28(s,1H),6.23(s,1H),6.11(d,1H),6.09(d,1H),6.00(d,1H).

Compound (1-3-23)

Fusing point: 92.10 DEG C

¹H-NMR(CDCl ₃；δppm):7.49(d,2H),7.41(d,2H),7.33(s,1H),7.21(d,2H),7.19(d,2H),7.08(s,1H),6.68(d,1H),6.56(s,1H),6.52(s,1H),6.40(m,2H),6.28(s,1H),6.23(s,1H),6.11(d,1H),6.09(d,1H),6.00(d,1H),2.46(s,3H).

Compound (1-3-40)

Fusing point: 134.96 DEG C

¹H-NMR(CDCl ₃；δppm):7.51(d,2H),7.45(d,2H),7.42(d,1H),7.21-7.13(m,8H),6.37(s,2H),6.21(s,1H),5.77(m,2H),5.68(m,1H),2.08(s,6H),1.94(s,3H).

Compound (1-2-1)

Fusing point: 162.64 DEG C

¹H-NMR(CDCl ₃；δppm):7.71(d,2H),7.66(m,4H),7.60(d,1H),7.51(d,2H),7.48(d,2H),7.22(d,2H),7.17(d,2H),6.38(d,2H),6.22(s,1H),5.78(d,2H),5.67(s,1H),2.09(s,3H),2.08(s,3H),1.95(s,3H).

Compound (1-3-13)

Fusing point: 115.29 DEG C

¹H-NMR(CDCl ₃；δppm):7.49(d,2H),7.40(s,1H),7.37(d,2H),7.18(d,2H),7.17(d,2H),7.02(s,1H),6.38(d,2H),6.16(s,1H),5.78(s,2H),5.62(s,1H),3.11(quin,1H),2.08(d,6H),1.92(s,3H),1.19(d,6H).

Compound (1-3-17)

Fusing point: 143.92 DEG C

¹H-NMR(CDCl ₃；δppm):7.64(d,2H),7.55(m,1H),7.48(m,3H),7.40(d,1H),7.22(d,2H),7.17(d,2H),6.49(m,1H),6.37(d,2H),6.20(dd,1H),5.94(dd,1H),5.78(td,2H),2.09(d,6H).

Compound (1-3-28)

Fusing point: 154.36 DEG C

¹H-NMR(CDCl ₃；δppm):7.52(d,2H),7.53(d,1H),7.44(d,2H),7.40(d,2H),7.23-7.11(m,7H),6.37(s,2H),6.21(s,1H),5.77(m,2H),5.68(m,1H),2.08(s,6H),1.94(s,3H).

Compound (1-3-34)

Fusing point: 153.47 DEG C

¹H-NMR(CDCl ₃；δppm):7.51(d,2H),7.45(d,2H),7.42(d,2H),7.21-7.13(m,8H),6.37(s,2H),6.21(s,1H),5.77(m,2H),5.68(m,1H),2.08(s,6H),1.94(s,3H).

Compound (1-3-50)

Fusing point: 185.86 DEG C

¹H-NMR(CDCl ₃；δppm):7.68(d,2H),7.52(d,2H),7.48(d,2H),7.39(dd,1H),7.28(d,1H),7.16-7.01(m,7H),6.71(m,1H),6.43(m,1H),6.36(s,2H),6.11(m,1H),5.77(t,2H),2.07(m,6H).

Compound (1-3-51)

Fusing point: 179.69 DEG C

¹H-NMR(CDCl ₃；δppm):7.68(d,2H),7.52(d,2H),7.48(d,2H),7.39(dd,1H),7.28(d,1H),7.16-7.01(m,7H),6.47(s,1H),6.36(s,1H),5.85(t,1H),5.77(t,2H),2.13(m,3H),2.07(m,6H).

Compound (1-3-52)

Fusing point: 171.97 DEG C

¹H-NMR(CDCl ₃；δppm):7.69(d,1H),7.52(d,2H),7.49(d,2H),7.40(dd,1H),7.28(d,1H),7.16-7.01(m,7H),6.71(dd,1H),6.62(td,1H),6.43(dd,1H),6.35(dd,1H),6.31(dd,1H),6.11(dd,1H),6.02(dd,2H).

Compound (1-3-58)

Fusing point: 114.44 DEG C

¹H-NMR(CDCl ₃；δppm):7.63(dd,2H),7.47(d,1H),7.27(d,1H),7.22(d,2H),7.18(d,2H),6.37(s,2H),6.20(s,1H),5.79(dd,2H),5.67(dd,2H),2.09(s,3H),2.08(s,3H),1.93(s,3H).

Compound (1-3-64)

Fusing point: 120.96 DEG C

¹H-NMR(CDCl ₃；δppm):7.63(dd,2H),7.47(d,2H),7.25(m,4H),7.19(d,2H),6.66(dd,1H),6.62(dd,1H),6.35(m,2H),6.19(s,1H),6.04(m,2H),5.66(t,1H),1.92(s,3H).

Compound (1-3-65)

Fusing point: 162.97 DEG C

¹H-NMR(CDCl ₃；δppm):7.62(d,2H),7.47(d,2H),7.25(m,4H),7.18(d,2H),6.64(dd,1H),6.48(dd,1H),6.39-6.32(m,2H),6.18(dd,1H),6.04(dd,1H),5.94(dd,1H),5.78(t,1H),2.08(s,3H).

Compound (1-3-66)

Fusing point: 93.43 DEG C

¹H-NMR(CDCl ₃；δppm):7.32(t,2H),7.23(t,2H),7.06(s,1H),7.02(m,2H),6.97(d,1H),6.37(d,2H),5.99(s,1H),5.61(d,2H),5.53(s,1H),2.49(s,3H),2.36(s,3H),2.08(d,6H),1.82(s,3H).

Compound (1-3-154)

Fusing point: 130.13 DEG C

¹H-NMR(CDCl ₃；δppm):7.63(t,4H),7.41(d,1H),7.30-7.17(m,7H),6.38(s,2H),5.78(d,2H),4.30(dd,1H),4.05(dd,1H),3.30(s,1H),2.84(t,1H),2.71(dd,1H),2.09(s,6H).

Compound (1-3-155)

Fusing point: 161.30 DEG C

¹H-NMR(CDCl ₃；δppm):7.62(d,4H),7.19(d,4H),7.01(s,2H),6.38(s,2H),5.78(s,2H),4.30(dd,2H),4.05(dd,2H),3.30(s,2H),2.84(t,2H),2.71(dd,2H),2.09(s,6H).

[embodiment 6]

By synthesizing compound (1-2-1) ~ (1-2-20) shown below and compound (1-3-1) ~ (1-3-182) with reference to the experimental implementation recorded in embodiment 1 ~ 5 and " 2. synthesis method ".

(synthesis of comparative compound)

According to following reaction formula synthesis comparative compound (R-1) i.e. [1,1'-xenyl]-4,4'-bis-synthesis of base pair (2-methacrylic ester), and obtain the colourless crystallization of comparative compound (R-1).

¹H-NMR(DMSO-d；δppm):7.24(d,4H),6.96(d,4H),6.41(d,2H),6.26(d,2H),1.98(s,6H).

The physical property of comparative compound (R-1) is as described below.Fusing point: 150.0 DEG C.

[comparative example 1]

(comparison of the solubleness in liquid-crystal composition)

Ratio with 0.3 % by weight adds compound (1-3-89) in following liquid-crystal composition A, heats 30 minutes at 50 DEG C.The solution of gained is at room temperature placed 2 days.Then, observe crystallization whether separate out by visual.On the other hand, for comparative compound (R-1), also observe in the same way.Result table 1 illustrate.In mark in table 2, "○" represents that crystallization is not separated out, and "×" represents crystallization.Known according to table 2, the solubleness of polymerizable compound of the present invention in liquid-crystal composition A is good.In addition, the composition of liquid-crystal composition A and ratio thereof are as described below.

The comparison of the solubleness of table 1. in liquid-crystal composition

7. the embodiment of Polymerizable composition

Compound in embodiment is the definition based on following table 2, is represented by mark.In table 2, the steric configuration relevant with Isosorbide-5-Nitrae-cyclohexylidene is trans.The numbering being positioned at the parantheses after mark in embodiment is corresponding with the numbering of compound.The mark of (-) refers to other liquid crystal compounds.The content (per-cent) of liquid crystal compounds is the weight percent (% by weight) based on liquid-crystal composition.Finally, the physics value of Polymerizable composition is concluded.Physical property measures according to the method recorded before, measured value (extrapolation) directly recorded.

Table 2 uses the expression method of the compound of mark

R-(A ₁)-Z ₁-.....-Z _n-(A _n)-R’

[embodiment 7]

Ratio with 0.3 % by weight adds following compound (1-3-1) in the composition.

NI＝101.2℃；Δn＝0.191；Δε＝7.8；η＝39.8mPa·s。

[embodiment 8]

Ratio with 0.25 % by weight adds following compound (1-3-12) in the composition.

NI＝103.3℃；Δn＝0.101；Δε＝4.6；η＝18.5mPa·s。

[embodiment 9]

Ratio with 0.1 % by weight adds following compound (1-3-54) in the composition.

[embodiment 10]

Ratio with 0.3 % by weight adds following compound (1-8-16) in the composition.

NI＝99.6℃；Δn＝0.118；Δε＝9.1；η＝36.0mPa·s。

[embodiment 11]

Ratio with 0.2 % by weight adds following compound (1-3-13) in the composition.

NI＝83.4℃；Δn＝0.104；Δε＝8.6；η＝22.9mPa·s。

[embodiment 12]

Ratio with 0.4 % by weight adds following compound (1-3-17) in the composition.

NI＝72.3℃；Δn＝0.074；Δε＝2.8；η＝13.8mPa·s。

[embodiment 13]

Ratio with 0.35 % by weight adds following compound (1-3-2) in the composition.

NI＝81.7℃；Δn＝0.065；Δε＝5.4；η＝19.1mPa·s。

[embodiment 14]

Ratio with 0.15 % by weight adds following compound (1-3-21) in this composition.

NI＝83.9℃；Δn＝0.132；Δε＝6.3；η＝11.7mPa·s。

[embodiment 15]

Ratio with 0.25 % by weight adds following compound (1-3-28) in the composition.

NI＝83.0℃；Δn＝0.105；Δε＝6.1；η＝12.0mPa·s。

[embodiment 16]

Ratio with 0.3 % by weight adds following compound (1-3-34) in the composition.

NI＝82.5℃；Δn＝0.100；Δε＝6.7；η＝12.4mPa·s。

[embodiment 17]

Ratio with 0.3 % by weight adds following compound (1-3-58) in the composition.

NI＝101.7℃；Δn＝0.193；Δε＝8.2；η＝40.3mPa·s。

[embodiment 18]

Following compound (1-3-1) and compound (1-3-12) is added in the composition respectively with the ratio of 0.2 % by weight.

NI＝79.9℃；Δn＝0.102；Δε＝8.6；η＝21.6mPa·s。

[embodiment 19]

Ratio with 0.3 % by weight adds following compound (1-3-56) in the composition.

NI＝100.8℃；Δn＝0.192；Δε＝8.2；η＝41.0mPa·s。

[embodiment 20]

Ratio with 0.25 % by weight adds following compound (1-3-57) in the composition.

NI＝100.5℃；Δn＝0.100；Δε＝4.6；η＝17.9mPa·s。

[embodiment 21]

Ratio with 0.1 % by weight adds following compound (1-3-64) in the composition.

NI＝97.8℃；Δn＝0.116；Δε＝9.0；η＝35.0mPa·s。

[embodiment 22]

Ratio with 0.3 % by weight adds following compound (1-3-65) in the composition.

NI＝80.2℃；Δn＝0.103；Δε＝8.7；η＝22.4mPa·s。

[embodiment 23]

Ratio with 0.2 % by weight adds following compound (1-3-56) in the composition.

NI＝79.4℃；Δn＝0.064；Δε＝5.7；η＝19.9mPa·s。

[embodiment 24]

Ratio with 0.2 % by weight adds following compound (1-3-56) and compound (1-3-65) in the composition.

NI＝80.6℃；Δn＝0.131；Δε＝7.7；η＝12.4mPa·s。

[embodiment 25]

Ratio with 0.3 % by weight adds following compound (1-3-57) in the composition.

NI＝81.9℃；Δn＝0.105；Δε＝6.3；η＝12.0mPa·s。

[embodiment 26]

Ratio with 0.3 % by weight adds following compound (1-3-64) in the composition.

NI＝81.3℃；Δn＝0.103；Δε＝7.4；η＝12.8mPa·s。

[embodiment 27]

Ratio with 0.3 % by weight adds following compound (1-2-1) in the composition.

NI＝101.2℃；Δn＝0.191；Δε＝7.8；η＝39.8mPa·s。

[embodiment 28]

Ratio with 0.25 % by weight adds following compound (1-3-23) in the composition.

NI＝103.3℃；Δn＝0.101；Δε＝4.6；η＝18.5mPa·s。

[embodiment 29]

Ratio with 0.1 % by weight adds following compound (1-3-40) in the composition.

NI＝86.7℃；Δn＝0.115；Δε＝5.7；η＝24.7mPa·s。

[embodiment 30]

Ratio with 0.3 % by weight adds following compound (1-3-50) in the composition.

NI＝99.6℃；Δn＝0.118；Δε＝9.1；η＝36.0mPa·s。

[embodiment 31]

Ratio with 0.2 % by weight adds following compound (1-3-51) in the composition.

NI＝83.4℃；Δn＝0.104；Δε＝8.6；η＝22.9mPa·s。

[embodiment 32]

Ratio with 0.4 % by weight adds following compound (1-3-52) in the composition.

NI＝72.3℃；Δn＝0.074；Δε＝2.8；η＝13.8mPa·s。

[embodiment 33]

Ratio with 0.35 % by weight adds following compound (1-3-66) in the composition.

NI＝81.7℃；Δn＝0.065；Δε＝5.4；η＝19.1mPa·s。

[embodiment 34]

Ratio with 0.15 % by weight adds following compound (1-3-154) in the composition.

NI＝83.9℃；Δn＝0.132；Δε＝6.3；η＝11.7mPa·s。

[embodiment 35]

Following compound (1-2-1) and compound (1-3-155) is added in the composition respectively with the ratio of 0.2 % by weight.

NI＝83.0℃；Δn＝0.105；Δε＝6.1；η＝12.0mPa·s。

[industry applications]

By making the Polymerizable composition of inclusion compound (1) and liquid-crystal composition be polymerized, make the liquid crystal display device with PSA isotype.Described polymerizable compound also can be used as the raw material of optically anisotropic body.

Claims

1. a polymerizable compound, it comprises 3 or 4 rings mutually also not closing of series connection, and has the polymerizability base of more than 3, and wherein at least one polymerizability base is tied with the ring key not being two ends.

2. polymerizable compound according to claim 1, it is represented by formula (1):

In formula (1),

P ¹, P ², P ³and P ⁴for polymerizability base;

A1, a3 and a4 be independently 0,1,2,3 or 4, a2 be 1,2,3 or 4, and a1, a2, a3 and a4 and be 3 to 10;

Ring A ²and ring A ³be independently 1, 4-phenylene, pyrimidine-2, 5-bis-base, pyridine-2, 5-bis-base, naphthalene-1, 2-bis-base, naphthalene-1, 3-bis-base, naphthalene-1, 4-bis-base, naphthalene-1, 5-bis-base, naphthalene-1, 6-bis-base, naphthalene-1, 7-bis-base, naphthalene-1, 8-bis-base, naphthalene-2, 3-bis-base, naphthalene-2, 6-bis-base, naphthalene-2, 7-bis-base, 1, 4-cyclohexylidene, 1, 4-phenylidene, tetrahydropyrans-2, 5-bis-base, or 1, 3-diox-2, 5-bis-base, in these rings, at least one hydrogen can through halogen, the alkyl of carbon number 1 ~ 12, the alkoxyl group of carbon number 1 ~ 12, at least one hydrogen is through the alkyl of the carbon number 1 ~ 12 of halogen substiuted, or at least one hydrogen replaced through the alkoxyl group of the carbon number 1 ~ 12 of halogen substiuted,

B1 is 0 or 1.

3. polymerizable compound according to claim 2, wherein in formula according to claim 2 (1),

P ¹, P ², P ²and P ⁴for acryloxy or methacryloxy;

B1 is 0 or 1.

4. polymerizable compound according to claim 1 and 2, it is represented by formula (1-1):

In formula (1-1),

P ⁵, P ⁶, P ⁷and P ⁸independent is acryloxy or methacryloxy;

D1 is 0 or 1.

5. polymerizable compound according to claim 1, its be by formula (1-1-1) or formula (1-1-2) any one represented by:

In formula (1-1-1) and formula (1-1-2),

G1 is 0,1 or 2; And

6. polymerizable compound according to claim 1 and 2, it is represented by formula (1-2) or formula (1-3):

In formula (1-2) and formula (1-3),

E1, e3 and e4 be independently 0,1 or 2, e2 be 1 or 2, and e1, e2, e3 and e4 and be 1 ~ 4; And

7. polymerizable compound according to claim 1 and 2, it is represented by formula (1-4) or formula (1-5):

In formula (1-4) and formula (1-5),

P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy;

E1 is 1 or 2, and e2 is 0,1 or 2;

8. polymerizable compound according to claim 7, wherein in formula (1-4) or formula (1-5), P ⁹, an e1 P ¹¹and P ¹⁴in at least one is acryloxy, and at least one is methacryloxy.

9. polymerizable compound according to claim 1 and 2, it is represented by formula (1-6) or formula (1-7):

In formula (1-6) and formula (1-7), P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy; And

Y ²for the alkyl of halogen, carbon number 1 ~ 5, the alkoxyl group of carbon number 1 ~ 5; F1 is 1 or 2, and f2 is 0,1 or 2.

10. polymerizable compound according to claim 9, wherein in formula (1-6) or formula (1-7), P ⁹, a f1 P ¹¹and P ¹⁴in at least one is acryloxy, and at least one is methacryloxy.

11. polymerizable compounds according to claim 1 and 2, it is represented by formula (1-8) or formula (1-9):

In formula (1-8) or formula (1-9), P ⁹, P ¹¹and P ¹⁴independent is acryloxy or methacryloxy; And g1 is 1 or 2.

12. 1 kinds of Polymerizable compositions, it contains the compound of at least one according to any one of claim 1 to 11.

13. Polymerizable compositions according to claim 12, at least one compound in its cohort also containing the compound be selected from represented by formula (2) ~ (4):

In formula (2) ~ (4),

R ¹¹and R ¹²independent is the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in described alkyl or alkenyl, and at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

Ring B ¹, ring B ², ring B ³, and ring B ⁴independent is Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene, the fluoro-Isosorbide-5-Nitrae-phenylene of 2-, 2,5-bis-fluoro-Isosorbide-5-Nitrae-phenylenes or pyrimidine-2,5-bis-base; And

14. Polymerizable compositions according to claim 12 or 13, at least one compound in its cohort also containing the compound be selected from represented by formula (5) ~ (7):

In formula (5) ~ (7),

R ¹³for the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in described alkyl or alkenyl, at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

L ¹¹and L ¹²independent is hydrogen or fluorine.

15. according to claim 12 to the Polymerizable composition according to any one of 14, at least one compound in its cohort also containing the compound be selected from represented by formula (8):

In formula (8),

R ¹⁴for the alkyl of carbon number 1 ~ 10 or the thiazolinyl of carbon number 2 ~ 10, in alkyl or alkenyl, at least one-CH ₂-can replace through-O-, and at least one hydrogen can replace through fluorine;

X ¹²for-C ≡ N or-C ≡ C-C ≡ N;

L ¹³and L ¹⁴independent is hydrogen or fluorine; And

I is 1,2,3 or 4.

16. 1 kinds of liquid crystal complex bodys, it is generated by the polymerization according to claim 12 to the Polymerizable composition according to any one of 15.

17. 1 kinds of optically anisotropic bodies, it is generated by the polymerization according to claim 12 to the Polymerizable composition according to any one of 15.

18. 1 kinds of liquid crystal display device, it contains according to claim 12 to the Polymerizable composition according to any one of 15 or liquid crystal complex body according to claim 15.

19. 1 kinds are selected from compound according to any one of claim 1 to 11, purposes according to claim 12 at least one in the cohort of the Polymerizable composition according to any one of 15 and liquid crystal complex body according to claim 16, and it is for liquid crystal display device.